CN104591301B - A kind of porous nano CoFe 2o 4preparation method - Google Patents

A kind of porous nano CoFe 2o 4preparation method Download PDF

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CN104591301B
CN104591301B CN201510018222.0A CN201510018222A CN104591301B CN 104591301 B CN104591301 B CN 104591301B CN 201510018222 A CN201510018222 A CN 201510018222A CN 104591301 B CN104591301 B CN 104591301B
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cofe
preparation
template
porous nano
molysite
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CN104591301A (en
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王晟
杜湘云
王田珍
柯旭
胡海龙
黄集森
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Nanjing Tech University
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Abstract

The invention discloses a kind of porous nano CoFe 2o 4preparation method, the method is (0.001% ~ 70%) in the mass percent of molysite, cobalt salt, alkali, deionized water, organic solvent and sublimable compound masterplate: (0.00001% ~ 70%): (0.001% ~ 55%): (0.001% ~ 90%): (0.001% ~ 90%): the ratio of (0.001% ~ 90%), the mixing solutions of molysite and cobalt salt and alkaline solution are reacted, obtains CoFe through abstraction and purification 2o 4colloidal sol; By CoFe 2o 4colloidal sol mixes through ultrasonic disperse with deionized water, add organic solvent and sublimable compound masterplate again, adopt the hot method reaction of water-organic solvent mixed solvent, after distillation removing mixed solvent, thermal treatment removes sublimable compound masterplate, again through cooling, grinding, washing, filtration, dry and grinding technics process, namely obtain porous nano CoFe 2o 4powder.The method is simple for process, invests little, is conducive to applying.

Description

A kind of porous nano CoFe 2o 4preparation method
Technical field
The present invention relates to a kind of porous nano CoFe 2o 4preparation method, belong to field of photocatalytic material.
Background technology
Along with the quickening of process of industrialization, energy dilemma and ecocrisis are day by day serious, and the exploitation of renewable new forms of energy receives much concern.Sun power, as a kind of clean energy, is the energy that inexhaustible, nexhaustible, pollution-free, cheap, world community all can freely be utilized peacefully, be also various renewable energy source as other energy such as biomass energy, wind energy, sea energy, water energy this.National governments all attach great importance to the exploitation of renewable energy source, and renewable energy source is the hot research field that various countries invest energetically.
Photocatalyst is the semiconductor material that a class develops sun power indispensability.At present, of a great variety by the semiconductor light-catalyst of scientists study, as TiO 2, CdS, SrTiO 3, RuO 2, ZnO and Fe 2o 3deng.CoFe 2o 4as a based semiconductor photocatalyst, have that good stability, indissoluble, environmental friendliness, band gap are narrow, aboundresources and the feature such as application cost is low, especially time with other semiconductors coupling, effectively can improve photocatalytic activity, be one of good photocatalyst of application prospect.
The Structure and Properties of material is closely related, structures shape performance, and the controlled synthesis of material structure is the hot research direction of material science, is the important means preparing high performance material.Research report at present about nano material controllable method for preparing is a lot.Since the people such as Penner in 1987 propose the template synthesis method of nano material, technique is simple, easy to operate, low power consumption and other advantages because having for template, receives and pays close attention to widely.Utilizing template, shape and the controlled nano material of size can be obtained by changing the diameter of template and other processing parameter.At present for the preparation of the materials such as nanocrystalline, nano thin-film, semi-conductor, nanotube and nano wire, in field of nano material preparation, there is consequence, become the important means preparing high-performance nano material.
CoFe 2o 4nanometer and porous improve CoFe 2o 4one of effective ways of photocatalysis efficiency.Prepare porous nano CoFe 2o 4can adopt template, template mainly contains microemulsion template, emulsion template, ionogenic surfactant template, nonionic surface active agent template, block copolymer template, composition template (polyoxyethylene lauryl ether and polyoxyethylene glycol) and monodisperse polymer particles template.By solgel reaction, CoFe 2o 4colloidal sol forms skeleton structure with secondary valence bond and template action, then takes solvent extration or high-temperature roasting method removing template, thus obtains the hole suitable with template size.But, use above-mentioned traditional Template preparation porous nano CoFe 2o 4time, be adopt roasting method or extraction process to remove template all to there is major defect.During roasting method removing template, because the temperature that will eliminate template is high, caving in of duct can be caused, make the porous nano CoFe made 2o 4semiconductor light-catalyst surface imperfection is too many, becomes the deathnium of electron-hole, reduces photocatalysis efficiency.Extraction rule is difficult to thoroughly eliminate template, makes porous nano CoFe 2o 4the purity drop of semiconductor light-catalyst, causes photocatalysis performance to decline.Therefore, how to prepare duct without caving in, surperficial zero defect, template noresidue and high-specific surface area porous nano CoFe 2o 4semiconductor light-catalyst is an important topic.
Easily remove because sublimate easily distils, therefore, the present invention is Template preparation CoFe by the compound adopting sublimation temperature suitable 2o 4colloidal sol, reheats and makes template distillation removing can obtain porous nano CoFe 2o 4.Compared with traditional template, the present invention adopt sublimate be template can prepare structure-controllable, duct without caving in, surperficial zero defect, template noresidue and the large porous nano CoFe of specific surface area 2o 4semiconductor light-catalyst.At present, about with sublimable compound for Template preparation porous nano CoFe 2o 4the method of semiconductor light-catalyst there is not yet bibliographical information, is porous nano CoFe 2o 4preparation open a new way, there is important practical significance.
Summary of the invention
A kind of porous nano CoFe of the present invention 2o 4preparation method, provide a kind of with molysite, cobalt salt, alkali, deionized water for raw material, prepare CoFe by stirring reaction 2o 4colloidal sol; CoFe 2o 4colloidal sol is after ultrasonic disperse, add organic solvent and sublimable compound template according to a certain percentage, after the hot method reaction of water-organic solvent mixed solvent, product removes sublimable compound template, cooling, washing, drying and grinding technics process through distillation removing mixed solvent, heat treated, namely obtains porous nano CoFe 2o 4.
A kind of porous nano CoFe of the present invention 2o 4preparation method, obtained porous nano CoFe 2o 4under visible ray and sunlight are the condition of light source, photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition can be directly used in, also by the method with other semiconductors coupling, obtained active higher photocatalyst further, under visible ray and sunlight are the condition of light source, for photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition;
A kind of porous nano CoFe of the present invention 2o 4preparation method, adopt following technical scheme:
1, by molysite, cobalt salt, alkali, deionized water, the mass percent of organic solvent and sublimable compound template is (0.001% ~ 70%): (0.00001% ~ 70%): (0.001% ~ 55%): (0.001% ~ 90%): (0.001% ~ 90%): the ratio of (0.001% ~ 90%), by molysite, one meromict of cobalt salt and the total consumption of deionized water, stirring and dissolving obtains the mixing solutions of molysite and cobalt salt, second half of total to alkali and deionized water consumption is mixed, stirring and dissolving obtains alkaline solution, under stirring, the mixing solutions of molysite and cobalt salt is added dropwise in alkaline solution, drip rear continuation stirring reaction 1 ~ 24h, product through centrifugation and washing operation and in triplicate, centrifugation obtains CoFe again 2o 4colloidal sol, by CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 2 ~ 10 mixes, be 20KHz ~ 1MHz by frequency, power is the ultrasonic wave dispersion 0.1h ~ 20h of 30W ~ 15KW, add organic solvent and sublimable compound template, at 100 ~ 250 DEG C, 0.5 ~ 20h is reacted by water-hot method of organic solvent mixed solvent, product is after distillation removing mixed solvent, 400 ~ 800 DEG C are warmed up to by the heat-up rate of per minute 0.5 ~ 3 DEG C, heat treated 0.5 ~ 24h removes sublimable compound template, again through cooling, grinding, washing, filter, drying and grinding technics process, namely porous nano CoFe is obtained 2o 4powder.
2, a kind of porous nano CoFe of the present invention 2o 4preparation method, its outstanding feature is: adopt traditional microemulsion template, emulsion template, ionogenic surfactant template, nonionic surface active agent template, block copolymer template, composition template (polyoxyethylene lauryl ether and polyoxyethylene glycol) and monodisperse polymer particles casting formwork, make CoFe by solgel reaction 2o 4colloidal sol forms skeleton structure with secondary valence bond and template action, when then taking solvent extration or high-temperature roasting method removing template, all there is major defect, can cause that duct caves in, surface imperfection, specific surface area are low and template residue problem, reduce photocatalysis efficiency; Compared with traditional template, when taking sublimate as template, sublimate easily distils and easily eliminates, and therefore, is Template preparation CoFe by the compound adopting sublimation temperature suitable 2o 4colloidal sol, reheat process removing sublimate template can obtain structure-controllable, duct without caving in, surperficial zero defect, template noresidue and the large porous nano CoFe of specific surface area 2o 4, be conducive to improving photocatalysis efficiency.
3, a kind of porous nano CoFe of the present invention 2o 4preparation method, the molysite reacting used is any one or more in iron trichloride, iron bromide, ferric sulfate, iron nitrate, ironic formiate, ironic acetate, ironic citrate and tartrate iron.
4, a kind of porous nano CoFe of the present invention 2o 4preparation method, the cobalt salt reacting used is any one or more in cobalt chloride, cobaltous bromide, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous formate, cobaltous acetate, citric acid cobalt and tartrate cobalt.
5, a kind of porous nano CoFe of the present invention 2o 4preparation method, the alkali reacting used is any one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, ammoniacal liquor and hydrated barta.
6, a kind of porous nano CoFe of the present invention 2o 4preparation method, the sublimable compound template of reacting used is any one or more in para benzoquinone, trimeric cyanamide, iodine, vulkacit H, camphor, anthraquinone, naphthalene, anthracene, trioxymethylene and triethylamine hydrochloride.
7, a kind of porous nano CoFe of the present invention 2o 4preparation method, the organic solvent reacting used is any one or more in methyl alcohol, ethanol, Virahol, ether, isopropyl ether, formic acid, acetic acid, methylene dichloride, chloroform, tetracol phenixin, acetone, pimelinketone, methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
8, a kind of porous nano CoFe of the present invention 2o 4preparation method, porous nano CoFe 2o 4preparation process in the frequency of ultrasonic disperser used be 20KHz ~ 1MHz, power is 30W ~ 15KW.
Embodiment
Here is a kind of porous nano CoFe of the present invention 2o 4the non-limiting example of preparation method.The providing of these examples is only used to the object illustrated, can not be interpreted as limitation of the invention.Because without departing from the spirit and scope of the present invention, many conversion can be carried out to the present invention.In these embodiments, unless stated otherwise, all per-cent all refers to mass percent.
Embodiment 1
Porous nano CoFe 2o 4preparation:
According to above-mentioned mass percent, by iron trichloride, iron bromide, rose vitriol, one meromict of cobaltous bromide and the total consumption of deionized water, stirring and dissolving obtains iron trichloride, iron bromide, the mixing solutions of rose vitriol and cobaltous bromide, second half of total to potassium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains potassium hydroxide solution, by iron trichloride under stirring, iron bromide, the mixing solutions of rose vitriol and cobaltous bromide is added dropwise in potassium hydroxide solution, drip rear continuation stirring reaction 2h, product through centrifugation and washing operation and in triplicate, centrifugation obtains CoFe again 2o 4colloidal sol, by CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 3 mixes, be 28KHz by frequency, power is the ultrasonic wave dispersion 1h of 2KW, add Virahol, benzene, after anthraquinone and vulkacit H, at 150 DEG C, 10h is reacted by water-hot method of organic solvent mixed solvent, product removes after desolventizing through distillation, 500 DEG C are warmed up to by the heat-up rate of per minute 1 DEG C, heat treated 10h at 500 DEG C, after removing anthraquinone and the sublimable compound template of vulkacit H, again through cooling, grinding, washing, filter, drying and grinding technics process, namely porous nano CoFe is obtained 2o 4powder.
Embodiment 2
Porous nano CoFe 2o 4preparation:
According to above-mentioned mass percent, by iron nitrate, ironic formiate, one meromict of citric acid cobalt and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the total consumption of deionized water, stirring and dissolving obtains iron nitrate, ironic formiate, the mixing solutions of citric acid cobalt and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, second half of total to sodium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains sodium hydroxide solution, by iron nitrate under stirring, ironic formiate, the mixing solutions of citric acid cobalt and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is added dropwise in sodium hydroxide solution, drip rear continuation stirring reaction 3h, product through centrifugation and washing operation and in triplicate, centrifugation obtains CoFe again 2o 4colloidal sol, by CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 4 mixes, with frequency be 68KHz, power be 3KW ultrasonic wave dispersion 2h, after adding ethanol, toluene, para benzoquinone and camphor, at 160 DEG C, 8h is reacted by water-hot method of organic solvent mixed solvent, product removes after desolventizing through distillation, 550 DEG C are warmed up to by the heat-up rate of per minute 0.5 DEG C, heat treated 8h at 550 DEG C, after removing para benzoquinone and the sublimable compound template of camphor, again through cooling, grinding, washing, filtration, dry and grinding technics process, namely obtain porous nano CoFe 2o 4powder.
Embodiment 3
Porous nano CoFe 2o 4preparation:
According to above-mentioned mass percent, by ferric sulfate, ironic citrate, one meromict of cobalt chloride and cobaltous acetate and the total consumption of deionized water, stirring and dissolving obtains ferric sulfate, ironic citrate, the mixing solutions of cobalt chloride and cobaltous acetate, second half of lithium hydroxide and hydrated barta and the total consumption of deionized water is mixed, stirring and dissolving obtains lithium hydroxide and hydrated barta mixing solutions, by ferric sulfate under stirring, ironic citrate, the mixing solutions of cobalt chloride and cobaltous acetate is added dropwise in lithium hydroxide and hydrated barta mixing solutions, drip rear continuation stirring reaction 4h, product through centrifugation and washing operation and in triplicate, centrifugation obtains CoFe again 2o 4colloidal sol, by CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 5 mixes, be 40KHz by frequency, power is the ultrasonic wave dispersion 2.5h of 1.5KW, add ethyl acetate, methyl ethyl ketone, acetone, naphthalene, after trioxymethylene and anthracene, at 170 DEG C, 6h is reacted by water-hot method of organic solvent mixed solvent, product removes after desolventizing through distillation, 600 DEG C are warmed up to by the heat-up rate of per minute 1.5 DEG C, heat treated 6h at 600 DEG C, removing naphthalene, after trioxymethylene and the sublimable compound template of anthracene, again through cooling, grinding, washing, filter, drying and grinding technics process, namely porous nano CoFe is obtained 2o 4powder.
Embodiment 4
Porous nano CoFe 2o 4preparation:
According to above-mentioned mass percent, by a meromict of iron trichloride and rose vitriol and the total consumption of deionized water, stirring and dissolving obtains the mixing solutions of iron trichloride and rose vitriol, second half of total to sodium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains sodium hydroxide solution, under stirring, the mixing solutions of iron trichloride and rose vitriol is added dropwise in sodium hydroxide solution, drip rear continuation stirring reaction 3.5h, through centrifugation and washing operation and in triplicate, then centrifugation obtains CoFe to product 2o 4colloidal sol; By CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 4.5 mixes, with frequency be 50KHz, power be 2.5KW ultrasonic wave dispersion 1.5h, after adding ethanol and anthracene, at 180 DEG C, 5h is reacted by water-hot method of organic solvent mixed solvent, product removes after desolventizing through distillation, 700 DEG C are warmed up to by the heat-up rate of per minute 2 DEG C, heat treated 5h at 700 DEG C, after the sublimable compound template of removing anthracene, again through cooling, grinding, washing, filtration, dry and grinding technics process, namely obtain porous nano CoFe 2o 4powder.

Claims (5)

1. a porous nano CoFe 2o 4preparation method, it is characterized in that: by molysite, cobalt salt, alkali, deionized water, the mass percent of organic solvent and sublimable compound template is (0.001% ~ 70%): (0.00001% ~ 70%): (0.001% ~ 55%): (0.001% ~ 90%): (0.001% ~ 90%): the ratio of (0.001% ~ 90%), by molysite, one meromict of cobalt salt and the total consumption of deionized water, stirring and dissolving obtains the mixing solutions of molysite and cobalt salt, second half of total to alkali and deionized water consumption is mixed, stirring and dissolving obtains alkaline solution, under stirring, the mixing solutions of molysite and cobalt salt is added dropwise in alkaline solution, drip rear continuation stirring reaction 1 ~ 24h, product through centrifugation and washing operation and in triplicate, centrifugation obtains CoFe again 2o 4colloidal sol, by CoFe 2o 4after the ratio that colloidal sol and the mass ratio of deionized water are 1: 2 ~ 10 mixes, be 20KHz ~ 1MHz by frequency, power is the ultrasonic wave dispersion 0.1h ~ 20h of 30W ~ 15KW, add organic solvent and sublimable compound template, the sublimable compound template added is para benzoquinone, trimeric cyanamide, iodine, vulkacit H, camphor, anthraquinone, naphthalene, anthracene, any one or more in trioxymethylene and triethylamine hydrochloride, at 100 ~ 250 DEG C, 0.5 ~ 20h is reacted again by water-hot method of organic solvent mixed solvent, product is after distillation removing mixed solvent, 400 ~ 800 DEG C are warmed up to by the heat-up rate of per minute 0.5 ~ 3 DEG C, heat treated 0.5 ~ 24h removes sublimable compound template, again through cooling, grinding, washing, filter, drying and grinding technics process, namely porous nano CoFe is obtained 2o 4powder.
2. preparation method according to claim 1, is characterized in that reacting molysite used is any one or more in iron trichloride, iron bromide, ferric sulfate, iron nitrate, ironic formiate, ironic acetate, ironic citrate and tartrate iron.
3. preparation method according to claim 1, is characterized in that reacting cobalt salt used is any one or more in cobalt chloride, cobaltous bromide, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous formate, cobaltous acetate, citric acid cobalt and tartrate cobalt.
4. preparation method according to claim 1, is characterized in that reacting alkali used is any one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, ammoniacal liquor and hydrated barta.
5. preparation method according to claim 1, is characterized in that reacting organic solvent used is any one or more in methyl alcohol, ethanol, Virahol, ether, isopropyl ether, formic acid, acetic acid, methylene dichloride, chloroform, tetracol phenixin, acetone, pimelinketone, methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
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