CN102503394A - Method for preparing series ferrite nano material with Fe2+ (ferrous ion) salt serving as iron source - Google Patents
Method for preparing series ferrite nano material with Fe2+ (ferrous ion) salt serving as iron source Download PDFInfo
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Abstract
A method for preparing a series ferrite nano material with Fe2+ (ferrous ion) salt serving as an iron source includes the steps: dissolving bivalent ion salt and bivalent or trivalent metal ion salt into dissolvent, wherein the dissolvent is deionized water, a mixture of deionized water and absolute ethyl alcohol, or mixed liquor of water and ethylene glycol; adding additives occupying 0-3% of the weight of the dissolvent and 0.01-1mol/L alkali liquor into liquor, and placing the liquor with the additives and the alkali liquor into an airtight pressure container; placing the container into constant-temperature heating equipment for constant-temperature heating for more than 3 hours within the range from 100 DEG C to 160 DEG C; and taking the container out and obtaining a target product after cooling, washing and drying. The method has the advantages that raw materials are easy to obtain, the method is low in cost without any oxidizers, simple in preparation process, convenient in operation and wide in applicable range, and the morphology and the particle size of the series ferrite nano material can be adjusted and controlled by changing the reaction temperature, the reaction time, types of additives and types of alkali, so that nano-scale crystal particles and micron-scale crystal particles are obtained.
Description
Technical field
The present invention relates to a kind of with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material.
Background technology
Wustite and composite nano materials thereof are one type of important multifunctional materials; Spinel ferrite is nanocrystalline to have good magnetics, magneto-optic, catalysis, absorbing property and high chemical stability; Characteristics such as with low cost, preparation technology is simple have been widely used in broadcast communication, information storage, space flight, control automatically, catalysis is synthetic and numerous areas such as medicine bioengineering.
On magnetics, can be used for the core of magnetic fluid, nuclear magnetic resonance, magnetic substance and make permanent magnet; Be applied to the magnetic thermotherapy in the biomedicine, medicine transmission; Can also make biosensor, X-former, electronic inductor; The information storage aspect can be used to make memory magnetic, electrochemistry holder; The absorbing property aspect can be used for microwave absorbing can also be used to make microwave device; Aspect electronic technology, can prepare end organ, electromagnetic interference protection cover.Because size, purity and the pattern of nanoparticle all have influence on the performance of material, the Ferrite Nanocrystalline Materials of different size of particles of therefore controlled preparation and pattern is the main field that the investigator pays close attention to.
Though up to the present multiple compound method begins to take shape; Like sol-gel method, the hot method of hydrothermal/solvent, template, deposition oxidation style, thermal decomposition method, ultrasonic method, sputter decomposition method, chemical Vapor deposition process, microemulsion method, rheological phase reaction method, molten-salt growth method or the like; But when synthesizing of ferrite; Depend on the ferric iron is source of iron more, and seldom uses ferrous iron to be source of iron.Make that like this scope of used source of iron is narrower, be unfavorable for this type of Development of Materials.Simultaneously, there is following problem in the ferrite nano material in order to the preparation of top method: 1) raw materials cost is high.Some reaction needed provides the solvent and the additive of more kind.2) part is high to operational requirement.There is complicated intermediate reaction in many methods, and to the reaction density ratio, pH value etc. has strict demand.3) temperature of reaction is high, and sintering temperature is generally all more than 200 ℃; 4) equipment cost is high, and higher temperature of reaction and complicated design route make production cost high or the like.
Summary of the invention
For overcoming above-mentioned shortcoming, the invention discloses a kind of with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material.Not only simple, with low cost, easy and simple to handle, the economic environmental protection of technology of the inventive method, and controllable granularity in the preparation process, high purity, processing are simple, are easy to industriallization.
Technical scheme of the present invention is to adopt the hydro-thermal synthetic system, and Fe2+ salt is distributed in the deionized water, adds auxiliary material, said mixture is placed in the airtight withstand voltage pasteurising vessel again, regulates temperature, time and realizes.The present invention realizes the control to particle morphology and particle diameter through the kind and the consumption of adjusting reaction time, temperature of reaction, reactant concn ratio and change additive.
A kind of with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material, it is characterized in that carrying out according to following steps:
(1) being dissolved in divalent iron salt and divalence or trivalent metal ion salts in the solvent, said solvent is a deionized water, or deionized water and absolute ethyl alcohol mixture, or water and ethylene glycol mixture;
(2) in solution, behind the additive and 0.01-1mol/L alkali lye of adding weight of solvent 0-3%, put it in the airtight pressure vessel;
(3) container is put into thermostatically heating equipment, in 100 ℃ to 160 ℃ scopes, thermostatically heating is more than 3 hours;
(4) take out container, after cooling, washing, drying, obtain target product.
Described divalent-metal ion salt comprises: all stable divalent-metal ion salt of second main group, first, second transition system; Described trivalent metal ion salts comprises: the 3rd main group, bismuth salt.
Said additive is any one in cats product, AS, neutral surface active agent, phenol, vinylformic acid (PAA), the oleyl amine.
Said alkali lye is that the oxyhydroxide of solubility is (like KOH, NaOH), a kind of in the ammoniacal liquor, thanomin, hexa-methylene Four Modernizations amine, urea.
The present invention has the following advantages:
1, raw material is simple, cost is low.Need not introduce external oxygenant and just can obtain corresponding ferrite, provide cost savings.
2, adopt one step hydro thermal method, preparation process is simple, and operation is convenient.
3, temperature required in the preparation process is 100 ℃-160 ℃, belongs to low-temperature hydrothermal-solvent thermal category, low for equipment requirements.
4, the present invention is applied widely, and through changing the temperature and the reaction times of reaction, the kind of additive and the kind of alkali can be regulated and control the pattern particle size of product, prepare nano level and micron-sized crystal grain.
Description of drawings
Fig. 1 a is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 1 deionized water, the sample transmission Photomicrograph that constant temperature 160 degree heating obtained under the situation in 5 hours;
Fig. 1 b is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 4 deionized waters, and PAA is a tensio-active agent, the sample transmission Photomicrograph that constant temperature 160 degree heating obtained under the situation in 5 hours;
Fig. 1 c is embodiment 14 deionized waters and 2: 5 solution of terepthaloyl moietie weight ratio, Manganous chloride tetrahydrate and ferrous sulfate weight ratio 1: 2, the sample scnning micrograph that constant temperature 160 degree heating obtained under the situation in 3 hours;
Fig. 1 d is embodiment 16 deionized waters and 2: 5 solution of terepthaloyl moietie weight ratio, Xiao Suangu and ferrous sulfate weight ratio 1: 2, and CTAB (CTAB) is a tensio-active agent, the sample scnning micrograph that constant temperature 160 degree heating obtained under the situation in 3 hours;
Fig. 1 e is Manganous chloride tetrahydrate and a ferrous sulfate weight ratio 1: 2 in embodiment 21 deionized waters, and CTAB (CTAB) is a tensio-active agent, the sample scanning electron photomicrograph that constant temperature 100 degree heating obtained under the situation in 4 hours;
Fig. 1 f is chromium chloride and a ferrous sulfate weight ratio 1: 2 in embodiment 22 deionized waters, and CTAB (CTAB) is a tensio-active agent, the sample scanning electron photomicrograph that constant temperature 100 degree heating obtained under the situation in 4 hours;
Fig. 1 g is a Xiao Suangu iron protochloride weight ratio 1: 2 in embodiment 5 deionized waters, the sample scanning electron photomicrograph that constant temperature 120 degree heating obtained under the situation in 5 hours;
Fig. 1 h is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 7 deionized waters, and phenol is tensio-active agent, the scanning electron photomicrograph that constant temperature 160 degree heating obtained under the situation in 6 hours.
Fig. 2 a is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 1 deionized water, the sample XRD diffraction spectra that constant temperature 160 degree heating obtained under the situation in 5 hours;
Fig. 2 b is Xiao Suangu and an iron protochloride weight ratio 1: 2 in embodiment 6 deionized waters, and PAA is a tensio-active agent, the sample XRD figure spectrum that constant temperature 120 degree heating obtained under the situation in 5 hours.
Fig. 3 a is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 9 deionized waters, and constant temperature 100 degree heating obtained blend sample XRD figure spectrum in 6 hours under the situation;
Fig. 3 b is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 7 deionized waters, and phenol is tensio-active agent, the sample XRD figure spectrum that constant temperature 160 degree heating obtained under the situation in 6 hours;
Fig. 3 c is Xiao Suangu and a ferrous sulfate weight ratio 1: 2 in embodiment 8 deionized waters, and phenol is tensio-active agent, the sample XRD figure spectrum that constant temperature 100 degree heating obtained under the situation in 6 hours;
Fig. 3 d is under 2: 5 conditions of embodiment 12 deionized waters and terepthaloyl moietie weight ratio, the sample XRD diffraction spectra that constant temperature 160 degree heating obtained under the situation in 6 hours.
Fig. 4 is embodiment 14 deionized waters and 2: 5 solution of terepthaloyl moietie weight ratio, Manganous chloride tetrahydrate and ferrous sulfate weight ratio 1: 2, the sample XRD diffraction spectra that constant temperature 160 degree heating obtained under the situation in 3 hours.
Fig. 5 a is embodiment 17 deionized waters and 2: 5 solution of terepthaloyl moietie weight ratio, Xiao Suangu and ferrous sulfate weight ratio 1: 2, and CTAB (CTAB) is a tensio-active agent, the sample XRD diffraction spectra that constant temperature 100 degree heating obtained under the situation in 4 hours;
Fig. 5 b is zinc sulfate and a ferrous sulfate weight ratio 1: 2 in embodiment 18 deionized waters, the sample XRD diffraction spectra that constant temperature 100 degree heating obtained under the situation in 4 hours;
Fig. 5 c is Manganous chloride tetrahydrate and a ferrous sulfate weight ratio 1: 2 in embodiment 19 deionized waters, the sample XRD diffraction spectra that constant temperature 100 degree heating obtained under the situation in 4 hours;
Fig. 5 d is embodiment 16 deionized waters and 2: 5 solution of terepthaloyl moietie weight ratio, Xiao Suangu and ferrous sulfate weight ratio 1: 2, and CTAB (CTAB) is a tensio-active agent, the sample XRD diffraction spectra that constant temperature 160 degree heating obtained under the situation in 3 hours.
Embodiment
Below in conjunction with accompanying drawing and case study on implementation invention is elaborated, but instance is not limited to the present invention, every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1:
With 5mmol Co (NO
3)
2With 10mmol FeSO
4Mix in the reaction kettle that adds 100ml with 10mmol vulkacit H and 70ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 5 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 2 a, its transmission microstructure is seen Fig. 1 a.
Embodiment 2:
With 5mmol Co (NO
3)
2, 10mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1gPAA and 10mmol vulkacit H 70ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 3:
With 3mmol Co (NO
3)
2With 6mmol FeSO
4Mix in the reaction kettle that adds 100ml with 6mmol vulkacit H 70ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 4
With 3mmol Co (NO
3)
2, 6mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1gPAA and 6mmol vulkacit H 70ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 5 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, product transmission microstructure is seen Fig. 1 b.
Embodiment 5
With 3mmol Co (NO
3)
2With 6mmol FeCl
2Mix in the reaction kettle that adds 100ml with 6mmol vulkacit H 70ml deionized water, put it in the thermostat container 120 ℃ of constant temperature 5 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the sample scanning spectra is seen Fig. 1 g.
Embodiment 6
With 3mmol Co (NO
3)
2, 6mmol FeCl
2Mix in the reaction kettle that adds 100ml with 1gPAA and 6mmol vulkacit H 70ml deionized water, put it in the thermostat container 120 ℃ of constant temperature 5 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 2 b.
Embodiment 7
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol phenol and 1mmol vulkacit H 70ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4-resol composite nanometer particle, the XRD figure of sample spectrum see that Fig. 3 b, electronic scanning photo see Fig. 1 h.
Embodiment 8:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol phenol and 1mmol vulkacit H 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4Nano particle contains small amount of impurities.The XRD figure spectrum of sample is seen Fig. 3 c.
Embodiment 9:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 3 a.
With 0.5mmol Co (NO
3)
2, 1mmol FeCl
2Gather ethanol 4000 (PEG) and 1mmol vulkacit H 70ml ethanol with 0.5g and mix in the reaction kettle that adds 100ml, put it in the thermostat container 160 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 11:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Gather ethanol 4000 (PEG) and 1mmol vulkacit H 50ml ethanol 20ml deionized water with 0.5g and mix in the reaction kettle that adds 100ml, put it in the thermostat container 160 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 12:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 6 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 3 d.
Embodiment 13:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Gather ethanol 4000 (PEG) and 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water with 0.5g and mix in the reaction kettle that adds 100ml, put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 14:
With 0.5mmol MnCl
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry product MnFe
2O
4Nano particle, the XRD figure of sample spectrum see that Fig. 4, scanning microstructure see Fig. 1 c.
Embodiment 15:
With 0.5mmol ZnSO
4, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water, put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry product ZnFe
2O
4Nano particle.
Embodiment 16:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water; Put it in the thermostat container 160 ℃ of constant temperature 3 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure of sample spectrum see that Fig. 5 d, scanning microstructure see Fig. 1 d.
Embodiment 17:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 1mmol vulkacit H 50ml terepthaloyl moietie 20ml deionized water; Put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry products C oFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 5 a.
Embodiment 18:
With 0.5mmol ZnSO
4, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry product ZnFe2O4 nano particle, the XRD figure spectrum of sample is seen Fig. 5 b.
Embodiment 19:
With 0.5mmol MnCl
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 1mmol vulkacit H 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry product MnFe
2O
4Nano particle, the XRD figure spectrum of sample is seen Fig. 5 c.
Embodiment 20:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 6mmolNaOH and 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 21:
With 0.5mmol MnCl
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 6mmolNaOH and 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry product MnFe
2O
4Nano particle, the scanning microstructure is seen Fig. 1 e.
Embodiment 22:
With 0.5mmol CdCl
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 6mmolNaOH and 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry products C dFe
2O
4Nano particle, the sample scanning spectra is seen Fig. 1 f.
Embodiment 23:
With 0.5mmol Co (NO
3)
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 3mmol urea and 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry products C oFe
2O
4Nano particle.
Embodiment 24:
With 0.5mmol MnCl
2, 1mmol FeSO
4Mix in the reaction kettle that adds 100ml with 0.5g CTAB (CTAB) and 3mmol urea and 70ml deionized water, put it in the thermostat container 100 ℃ of constant temperature 4 hours, through cooling, washing, dry product MnFe
2O
4Nano particle.
Claims (4)
1. with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material, it is characterized in that carrying out according to following steps:
(1) being dissolved in divalent iron salt and divalence or trivalent metal ion salts in the solvent, said solvent is a deionized water, or deionized water and absolute ethyl alcohol mixture, or water and ethylene glycol mixture;
(2) in solution, behind the additive and 0.01-1mol/L alkali lye of adding 0-3%, put it in the airtight pressure vessel;
(3) container is put into thermostatically heating equipment, in 100 ℃ to 160 ℃ scopes, thermostatically heating is more than 3 hours;
(4) take out container, after cooling, washing, drying, obtain target product.
2. according to claim 1 with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material: it is characterized in that: described divalent-metal ion salt comprises: all stable divalent-metal ion salt of second main group, first, second transition system; Trivalent metal ion salts comprises: the 3rd main group, bismuth salt.
3. according to claim 1 with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material.It is characterized in that: said additive is any one in cats product, AS, neutral surface active agent, phenol, vinylformic acid, the oleyl amine.
4. according to claim 1 with Fe
2+Salt is the method that source of iron prepares serial ferrite nano material.It is characterized in that: said alkali lye is a kind of in the oxyhydroxide, ammoniacal liquor, thanomin, hexa-methylene Four Modernizations amine, urea of solubility.
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| CN103426586A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Method for preparing zinc ferrite water-based nanometer magnetic fluid |
| CN105772020A (en) * | 2016-04-05 | 2016-07-20 | 中国地质大学（武汉） | Preparation method for manganese-doped magnetic ferrite microsphere with excellent fenton catalytic performance |
| CN107032412A (en) * | 2017-04-21 | 2017-08-11 | 哈尔滨工业大学 | A kind of preparation method of Conjugate ferrite magnetic nanoparticle |
| CN111533177A (en) * | 2020-04-28 | 2020-08-14 | 中国人民解放军陆军装甲兵学院 | Submicron hollow cobalt ferrite wave-absorbing material and preparation method thereof |
| CN112408498A (en) * | 2020-11-26 | 2021-02-26 | 上海颜钛实业有限公司 | Spinel type ferrite CoFe2O4Hydrothermal preparation method of nano powder |
| CN114073959A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Butene oxidative dehydrogenation catalyst and preparation method and application thereof |
| CN115739178A (en) * | 2022-09-08 | 2023-03-07 | 河北科技大学 | Preparation method and application of phenolic foam loaded manganese ferrite catalyst |
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| CN103426586A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Method for preparing zinc ferrite water-based nanometer magnetic fluid |
| CN105772020A (en) * | 2016-04-05 | 2016-07-20 | 中国地质大学（武汉） | Preparation method for manganese-doped magnetic ferrite microsphere with excellent fenton catalytic performance |
| CN105772020B (en) * | 2016-04-05 | 2019-08-23 | 中国地质大学（武汉） | A kind of preparation method of the additive Mn magnetic ferrites microballoon with good Fenton catalytic performance |
| CN107032412A (en) * | 2017-04-21 | 2017-08-11 | 哈尔滨工业大学 | A kind of preparation method of Conjugate ferrite magnetic nanoparticle |
| CN111533177A (en) * | 2020-04-28 | 2020-08-14 | 中国人民解放军陆军装甲兵学院 | Submicron hollow cobalt ferrite wave-absorbing material and preparation method thereof |
| CN114073959A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Butene oxidative dehydrogenation catalyst and preparation method and application thereof |
| CN114073959B (en) * | 2020-08-19 | 2023-08-29 | 中国石油化工股份有限公司 | Butene oxidative dehydrogenation catalyst and preparation method and application thereof |
| CN112408498A (en) * | 2020-11-26 | 2021-02-26 | 上海颜钛实业有限公司 | Spinel type ferrite CoFe2O4Hydrothermal preparation method of nano powder |
| CN115739178A (en) * | 2022-09-08 | 2023-03-07 | 河北科技大学 | Preparation method and application of phenolic foam loaded manganese ferrite catalyst |
| CN115739178B (en) * | 2022-09-08 | 2024-03-26 | 河北科技大学 | Preparation method and application of phenolic foam supported manganese ferrite catalyst |
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