CN105198006A - Application of porous cobaltosic oxide - Google Patents
Application of porous cobaltosic oxide Download PDFInfo
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- CN105198006A CN105198006A CN201510565368.7A CN201510565368A CN105198006A CN 105198006 A CN105198006 A CN 105198006A CN 201510565368 A CN201510565368 A CN 201510565368A CN 105198006 A CN105198006 A CN 105198006A
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- Prior art keywords
- pollen
- porous
- cobalt
- tricobalt tetroxide
- cobaltosic oxide
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001868 cobalt Chemical class 0.000 claims description 18
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011246 composite particle Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000010907 mechanical stirring Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000012423 maintenance Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- BGORGFZEVHFAQU-UHFFFAOYSA-L cobalt(2+);sulfate;hydrate Chemical compound O.[Co+2].[O-]S([O-])(=O)=O BGORGFZEVHFAQU-UHFFFAOYSA-L 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 241000220317 Rosa Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 3
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 238000002156 mixing Methods 0.000 description 13
- 239000003981 vehicle Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an application of porous cobaltosic oxide. The porous cobaltosic oxide is in a porous hollow elliptic shape, relatively high in specific surface area, rich in pores, adjustable in pore size, capable of being used as a high-performance super capacitor electrode material, an automobile tail gas treatment material and an adsorption material.
Description
Technical field
The invention discloses a kind of application of porous tricobalt tetroxide, belong to inorganic salt porous material applied technical field.
Background technology
Along with socioeconomic development, people more and more pay close attention to ecotope and green energy resource.The pollutents such as the carbon monoxide in vehicle exhaust, hydrocarbon polymer can cause photo-chemical smog etc.Therefore, vehicle exhaust is directly discharged in air, huge to environmental hazard, have a strong impact on the life security of people.
Tricobalt tetroxide has spinel crystal structure, a kind of important magneticsubstance, P-type transition metal oxide, show peculiar process based prediction model in fields such as electricity, magnetic, air-sensitive, catalysis, be widely used in the key areas such as lithium ion battery electrode material, magneticsubstance, heterogeneous catalyst, vehicle maintenance service.Such as: tricobalt tetroxide can be used as the electrode materials of ultracapacitor.Ultracapacitor, as a kind of novel energy-storing device, comes into one's own day by day.Compared with now widely used various energy storage material, ultracapacitor charge/discharge rates and efficiency are better than once or secondary cell.
The process based prediction model of tricobalt tetroxide is comparatively large by the impact of pattern, size and structure, and then affects its application performance.In recent years, the tricobalt tetroxide material with different-shape causes the great interest of people, adopts the different preparation methods such as mist projection granulating, microemulsion precipitation, sol-gel method, vapor deposition method in succession to synthesize nanometer ball, nano wire, nanometer rod, nanotube, nanofiber, nanocubes, hollow ball, flower-like microsphere, garland shape tricobalt tetroxide etc.
Chinese patent CN103011306B has invented a kind of method preparing nanometer-level cube-like cobaltosic oxide, by a certain amount of porous carbon dispersion in deionized water, join after ultrasonic disperse and fill cobalt salt, in the reactor of urea and deionized water mixing solutions, after being fully uniformly mixed, reactor is placed in baking oven, room temperature is naturally cooled to after hydro-thermal reaction certain hour, reaction product centrifugation for several times, after water washing process, obtain cubic cobaltosic oxide powder, this cubic cobaltosic oxide powder can obtain porous nano level cubic tricobalt tetroxide after high-temperature calcination in atmosphere further, Chinese patent CN102887548B has invented a kind of sea urchin shape hierarchy cobaltosic oxide nano ball and preparation method thereof, is mixed by cobalt chloride solution, add urea with glycerol, reaction, removal of impurities, calcining, obtains sea urchin shape hierarchy cobaltosic oxide nano ball, Chinese patent CN101913659B has invented a kind of preparation method of battery-grade cobaltosic oxide, with deionized water, cobalt raw material and precipitation agent is made into cobalt liquor respectively, adopt even phase crystallized precipitation legal system for presoma, through washing, dehydration, directly by moisture filter cake dress alms bowl, adopts low temperature dewatering phase transformation calcination to control grain fineness number and crystal morphology through high temperature nodularization calcining again, then through mechanical disintegration classification activation treatment, finally carry out the removal of magneticmetal foreign matter, finally obtain the spherical battery-grade cobaltosic oxide of class, Chinese patent CN102249348B has invented a kind of preparation method of hexagonal sheet tricobalt tetroxide, cobalt raw material, highly basic saturated solution is mixed with fusing assistant, obtains sintered material after oven dry, after described sintered material pulverizing, roasting, through naturally cooling, obtain sinter, described sinter is placed in 0.1 ~ 2.0M hydrochloric acid soak, after washing and filtering, obtains tricobalt tetroxide hexagonal sheet to wet product, the product that wet by described tricobalt tetroxide hexagonal sheet obtains product hexagonal sheet tricobalt tetroxide after drying.
Prior art can prepare the tricobalt tetroxide of various different-shape, but has used a large amount of organic solvents, is unfavorable for large-scale production and contaminate environment; Be used as the electrode materials of electrical condenser simultaneously, catalysis aspect, absorption aspect also need tricobalt tetroxide to have higher specific surface area and abundant gap structure.Therefore, develop a kind of raw material be easy to get, be easy to mass-producing synthesis, there is high specific surface area, abundant gap structure tricobalt tetroxide material has great importance.
Summary of the invention
The object of the present invention is to provide a kind of purposes of porous tricobalt tetroxide, porous tricobalt tetroxide novel structure disclosed by the invention is unique, have high specific surface area, abundant gap structure, method is simple and safe, be easy to suitability for industrialized production, it is simpler that template removes technique, without the need to using other chemical reagent, simplifying technique, having saved production cost, product purity is high, can be used as high-performance super capacitor electrode materials, vehicle maintenance service material and sorbing material.
To achieve the above object of the invention, the technical solution used in the present invention is:
Porous tricobalt tetroxide is preparing the application in capacitor electrode material.
Porous tricobalt tetroxide is preparing the application in vehicle maintenance service material.
Porous tricobalt tetroxide disclosed by the invention is prepared by following methods:
(1) at room temperature, added by pollen in distilled water, stirring, ultrasonic disperse obtain mixture; After said mixture centrifugation, get solids and add in dehydrated alcohol, stir, carry out centrifugal treating after ultrasonic disperse, dry centrifugal after solids, obtain the pollen of surperficial removal of impurities process;
(2) pollen getting surperficial removal of impurities process joins in distilled water, then adds inorganic cobalt salt, stirring, ultrasonic vibration; Then add quadrol, mechanical stirring obtains mixed solution; The described pollen of surperficial removal of impurities process and the weight ratio of inorganic cobalt salt are (80 ~ 5): 1;
(3) tensio-active agent is added in alkaline solution, add in the mixed solution of step (2) after stirring, stir; Then, at 5 ~ 90 DEG C, drip hydrazine hydrate, stir 0.5 ~ 24 hour; Then obtain solids through Magneto separate, solids, after distillation washing, dehydrated alcohol are washed, is dried and is obtained cobaltosic oxide precursor; By the roasting 1 ~ 8 hour at 200 ~ 290 DEG C of above-mentioned cobaltosic oxide precursor, obtain cobaltosic oxide powder composite particles; By the roasting 2 ~ 6 hours at 300 ~ 500 DEG C of above-mentioned cobaltosic oxide powder composite particles, obtain porous tricobalt tetroxide.
In the present invention, pollen is porous Pollen Brassicae campestris; Rape is at China's establishing in large scale, it not only can become beautiful landscape, yearning, vegetable seed oil expression also can be that the dining table of people increases taste, and Pollen Brassicae campestris is easy to get especially, for method of the present invention, significantly can reduce the preparation cost of porous tricobalt tetroxide, be conducive to the cost reducing end product, be not only conducive to enterprise and produce, more favourable to human consumer.
In technique scheme, described inorganic cobalt salt is one or more in cobaltous acetate, acetate hydrate cobalt, cobalt chloride, hydrated cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nitric hydrate cobalt, rose vitriol, cobalt sulfate hydrate.
In technique scheme, in step (1), the described ultrasonic disperse time is 5 ~ 30 minutes; The mass ratio of pollen and distilled water is 1: (4 ~ 100), and the mass ratio of solids and dehydrated alcohol is 1: (4 ~ 100).In order to better remove the impurity on pollen surface, can Ethanol Treatment 3 ~ 6 times be used, then under 30 ~ 60 DEG C of conditions, dry centrifugal thing.
In technique scheme, in step (2), the pollen of surperficial removal of impurities process and distilled water mass ratio are 1: (5 ~ 20); After adding inorganic cobalt salt, stir 10 ~ 120 minutes, ultrasonic vibration 2 ~ 5 minutes; Then add quadrol, mechanical stirring obtains mixed solution in 10 ~ 30 minutes.
In technique scheme, in step (3), tensio-active agent is added in alkaline solution, stir and add in the mixed solution of step (2) after 5 ~ 10 minutes, stir 5 ~ 60 minutes.
In technique scheme, in step (3), in order to obtain cleaner cobaltosic oxide precursor, solids washes 3 ~ 5 times through distillation washing, dehydrated alcohol; Then dry under 40 ~ 60 DEG C of conditions.
In technique scheme, in step (2), the mol ratio of described quadrol and inorganic cobalt salt is 1: (1 ~ 4).
In technique scheme, in step (3), the consumption of described tensio-active agent is 3% ~ 20% of pollen quality; Described alkaline solution is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution; In described alkaline solution, the molar weight of alkali and the molar weight of inorganic cobalt salt are than being (40 ~ 90): 1; The molar weight of described hydrazine hydrate and the molar weight of inorganic cobalt salt are than being (300 ~ 550): 1; Tensio-active agent is PVP, cetyl trimethylammonium bromide or polyoxyethylene glycol.
In technique scheme, kinds of surfactants is ionogenic surfactant PVP, cetyl trimethylammonium bromide, or nonionic surface active agent polyoxyethylene glycol.
In technique scheme, the product obtained is Porous hollow ball-type, and specific surface area is higher, hole is abundanter, therefore the present invention is preferably according to the porous tricobalt tetroxide that aforesaid method prepares, porous tricobalt tetroxide is elliposoidal, and particle diameter is 6 ~ 10 μm, specific surface area 91 ~ 120m
2/ g, surface mesh is of a size of 200 ~ 600nm.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention makes public for the first time and utilizes pure biological pollen to be template, has the features such as green, natural, wide material sources, and it is comparatively simple that template removes technique, and without the need to using other chemical reagent, simplifying technique, having saved production cost, product purity is high; The product obtained is Porous hollow ball-type, and specific surface area is higher, hole is abundanter, has unexpected property.
(2) porous tricobalt tetroxide disclosed by the invention is Porous hollow spheroid shape, and specific surface area is higher, hole is abundanter, and pore size is adjustable, can be used as high-performance super capacitor electrode materials, vehicle maintenance service material and sorbing material.
Accompanying drawing explanation
Fig. 1 is the EDX spectrogram of porous tricobalt tetroxide in embodiment one;
Fig. 2 is the SEM spectrogram of porous tricobalt tetroxide in embodiment one;
Fig. 3 is the SEM spectrogram of porous tricobalt tetroxide in embodiment two;
Fig. 4 is the SEM spectrogram of porous tricobalt tetroxide in embodiment three;
Fig. 5 is the SEM spectrogram of porous tricobalt tetroxide in embodiment four.
Embodiment
Below in conjunction with embodiment, accompanying drawing, the invention will be further described:
Embodiment one
At room temperature, the porous Pollen Brassicae campestris of 5g is joined in 50mL distilled water, after stirring 30min, ultrasonic disperse 5 ~ 30min.After said mixture centrifugation, then add 50mL dehydrated alcohol, repeat above-mentioned steps 3 times, in order to fully to remove the impurity on its surface.Then, the baking oven product after centrifugal being put into 30 DEG C is dried.Under room temperature, get the good pollen of 1g pre-treatment and join in 10mL distilled water, then add 1mmol cobaltous acetate, ultrasonic vibration 3min after stirring 10min, then add 0.5g quadrol, mechanical stirring 10min obtains mixing solutions.Under room temperature, the concentration PVP of 0.2g being joined 20mL is in the NaOH aqueous solution of 2mol/L, stirs 6min.Solution after stirring slowly is instilled in mixing solutions, mechanical stirring 10min.The solution of above-mentioned mixing is heated to 65 DEG C, then slowly instills the hydrazine hydrate of 20mL, stir 1h.Adopt magnetic separation technique to be separated by product after reacting completely, then clean 3 times respectively with distilled water and dehydrated alcohol.Then product is dried under 40 DEG C of conditions, porous tricobalt tetroxide precursor can be obtained.By the roasting 1 hour at 200 DEG C of the porous tricobalt tetroxide precursor that obtains, obtain cavernous carbon/cobaltosic oxide powder composite particles.By the roasting 3 hours at 300 DEG C of the composite particles that obtains, obtain cavernous cobaltosic oxide powder.
Accompanying drawing 1 is the EDX spectrogram of above-mentioned porous tricobalt tetroxide; As can be seen from the figure, Co atom, O atom and C atom is had in product.Wherein, the atomic ratio of Co:O is about 3:4, with target product Co
3o
4quite, result shows, through calcining, product is porous tricobalt tetroxide.
Accompanying drawing 2 is the SEM spectrogram of above-mentioned porous tricobalt tetroxide; As can be seen from the figure, product morphology is more regular, substantially maintains the pattern of original Pollen Brassicae campestris.The size of product about 8 μm.Result shows, can be prepared the elliposoidal tricobalt tetroxide of porous by the simple method of the present invention.
Embodiment two
Under room temperature, the Pollen Brassicae campestris of 10g is joined in 80mL, after stirring 40min, ultrasonic disperse 20min.After said mixture centrifugation, then add 40mL dehydrated alcohol, repeat above-mentioned steps 4 times, in order to fully to remove the impurity on its surface.Then, the baking oven product after centrifugal being put into 45 DEG C is dried.Under room temperature, get the good pollen of 2g pre-treatment and join in 30mL distilled water, then add the hydrated cobalt chloride of 1.5mmol, ultrasonic vibration 3min after stirring 65min, then add the quadrol of 4g, mechanical stirring 18min obtains mixing solutions.Under room temperature, the concentration poly(oxyethylene glycol) 400 of 0.3g being joined 30mL is in the NaOH solution of 3mol/L, stirs 7min.Solution after stirring slowly is dropped in mixing solutions, mechanical stirring 40min.The solution of above-mentioned mixing is heated to 70 DEG C, then slowly instills the hydrazine hydrate of 25mL, stir 8h.Adopt magnetic separation technique to be separated by product after reacting completely, then clean 3 times respectively with distilled water and dehydrated alcohol.Then product is dried under 45 DEG C of conditions, porous tricobalt tetroxide precursor can be obtained.By the roasting 2 hours at 260 DEG C of porous tricobalt tetroxide precursor, obtain cavernous carbon/cobaltosic oxide powder composite particles.Composite particles roasting 4 hours at 450 DEG C, obtains cavernous cobaltosic oxide powder.
Accompanying drawing 3 is the SEM spectrogram of above-mentioned porous tricobalt tetroxide; As can be seen from the figure, product morphology is more regular, substantially maintains the pattern of original Pollen Brassicae campestris.The size of product about 10 μm.Result shows, can be prepared the elliposoidal tricobalt tetroxide of porous by the simple method of the present invention.
Embodiment three
Under room temperature, the Pollen Brassicae campestris of 15g is joined in 80mL distilled water, after stirring 45min, ultrasonic disperse 25min.After said mixture centrifugation, then add 100mL dehydrated alcohol, repeat above-mentioned steps 5 times, in order to fully to remove the impurity on its surface.Then, the baking oven product after centrifugal being put into 60 DEG C is dried.Under room temperature, get the good pollen of 10g pre-treatment and join in 65mL distilled water, then add 2mmol cobalt sulfate hydrate, ultrasonic vibration 5min after stirring 25min, then add 4g quadrol, mechanical stirring 15min obtains mixing solutions.Under room temperature, the concentration PVP of 0.5g being joined 40mL is in the NaOH solution of 3mol/L, stirs 7min.Solution after stirring slowly is instilled in mixing solutions, mechanical stirring 15min.Above-mentioned mixing solutions is heated to 75 DEG C, then slowly instills the hydrazine hydrate of 35mL, stir 2h.Adopt magnetic separation technique to be separated by product after reacting completely, then clean 4 times respectively with distilled water and dehydrated alcohol.Then product is dried under 45 DEG C of conditions, porous tricobalt tetroxide precursor can be obtained; Roasting 2 hours at 270 DEG C, obtains cavernous carbon/cobaltosic oxide powder composite particles, and composite particles roasting 4 hours at 500 DEG C, obtains cavernous cobaltosic oxide powder.
Accompanying drawing 4 is the SEM spectrogram of above-mentioned porous tricobalt tetroxide; As can be seen from the figure, product morphology is more regular, substantially maintains the pattern of original Pollen Brassicae campestris.Have a small amount of particle to present obviously hollow structure, show, product is a kind of hollow structure tricobalt tetroxide of porous.The size of product about 8 μm.Result shows, can be prepared the elliposoidal tricobalt tetroxide of porous by the simple method of the present invention.
Embodiment four
Under room temperature, the Pollen Brassicae campestris of 20g is joined in 200mL distilled water, after stirring 60min, ultrasonic disperse 30min.After said mixture centrifugation, then add 250mL dehydrated alcohol, repeat above-mentioned steps 3 times, in order to fully to remove the impurity on its surface.Then, the baking oven product after centrifugal being put into 55 DEG C is dried.Under room temperature, get the good pollen of 10g pre-treatment and join in 65mL distilled water, then add 3mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, ultrasonic vibration 4min after stirring 80min, then add 5g quadrol, mechanical stirring 20min obtains mixing solutions.Under room temperature, the concentration CTAB of 0.6g being joined 60mL is in the KOH solution of 4mol/L, stirs 10min.Solution after stirring slowly is instilled in mixing solutions, mechanical stirring 55min.The solution of above-mentioned mixing is heated to 80 DEG C, then slowly instills the hydrazine hydrate of 40mL, stir 18h.Adopt magnetic separation technique to be separated by product after reacting completely, then clean 5 times respectively with distilled water and dehydrated alcohol.Then dried under 60 DEG C of conditions by product, can obtain porous tricobalt tetroxide precursor, roasting 5 hours at 270 DEG C, obtains cavernous carbon/cobaltosic oxide powder composite particles; Composite particles roasting 6 hours at 450 DEG C, obtains cavernous cobaltosic oxide powder.
Accompanying drawing 5 is the SEM spectrogram of above-mentioned porous tricobalt tetroxide; As can be seen from the figure, product morphology is more regular, substantially maintains the pattern of original Pollen Brassicae campestris.Have a small amount of particle to present obviously hollow structure, show, product is a kind of hollow structure tricobalt tetroxide of porous.The size of product about 7 μm.Result shows, can be prepared the elliposoidal tricobalt tetroxide of porous by the simple method of the present invention.
The sign of above-mentioned porous tricobalt tetroxide is in table 1, illustrate that porous tricobalt tetroxide prepared by the present invention is Porous hollow spheroid shape, specific surface area is higher, hole is abundanter, and pore size is adjustable, can be used as high-performance super capacitor electrode materials, vehicle maintenance service material and sorbing material.
Porous tricobalt tetroxide performance perameter in table 1 embodiment
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | |
| Specific surface area/m 2.g -1 | 118 | 112 | 101 | 92 |
| Mesh size/nm | 220 | 340 | 560 | 580 |
| Particle diameter/μm | 6 | 10 | 8 | 7 |
Embodiment five
Vehicle exhaust test experiments method: when porous tricobalt tetroxide material of the present invention is used as vehicle maintenance service, gets a certain amount of porous tricobalt tetroxide, pass into the reactant gases of simulation, composition (volume percent) is 1%CO, 19%O
2, all the other use N
2gas balances, and the flow velocity of reactant gases is 100ml/min, the gas composition gas chromatographic detection of reactor outlet.According to gas chromatographic detection result, the CO transformation efficiency under differing temps can be obtained, i.e. the absorption degradation rate of the many vehicle exhausts of porous tricobalt tetroxide, in table 2.Can find out that porous tricobalt tetroxide specific surface area of the present invention is higher, hole is abundanter, effectively can process vehicle exhaust.
Under table 2 differing temps, porous tricobalt tetroxide is to the transformation efficiency of carbon monoxide
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | |
| 350℃ | 90.7% | 87.6% | 70.6% | 64.2% |
| 400℃ | 94.2% | 92.1% | 88.1% | 86.2% |
| 500℃ | 99.8% | 98.2% | 88.4% | 87.2% |
| 550℃ | 99.9% | 99.9% | 99.8% | 99.9% |
Embodiment six
The experimental technique of capacitance electrode: when porous tricobalt tetroxide material is used for capacitor electrode material, there is higher specific storage, specific experiment method evenly applies nickel screen after being mixed with acetylene black, tetrafluoroethylene (mass ratio 6: 3: 1) by porous tricobalt tetroxide, is prepared into 1cm after Air drying
2electrode, then by this application of electrode in ultracapacitor, test its specific storage, in table 3 once increasing under current density condition.Can find out that porous tricobalt tetroxide specific surface area of the present invention is higher, hole is abundanter, be conducive to entering and moving of electrolyte ion, electrode materials prepared therefrom is applied to ultracapacitor and has higher specific storage.
Ultracapacitor specific storage under the different current density of table 3
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | |
| 0.5 A/g | 781 F/g | 721 F/g | 706F/g | 630 F/g |
| 5 A/g | 421 F/g | 412 F/g | 395 F/g | 350 F/g |
| 8 A/g | 380 F/g | 360 F/g | 326 F/g | 319 F/g |
Claims (8)
1. porous tricobalt tetroxide is preparing the application in vehicle maintenance service material; Described porous tricobalt tetroxide is prepared by following methods:
(1) at room temperature, added by pollen in distilled water, stirring, ultrasonic disperse obtain mixture; After said mixture centrifugation, get solids and add in dehydrated alcohol, stir, carry out centrifugal treating after ultrasonic disperse, dry centrifugal after solids, obtain the pollen of surperficial removal of impurities process;
(2) pollen getting surperficial removal of impurities process joins in distilled water, then adds inorganic cobalt salt, stirring, ultrasonic vibration; Then add quadrol, mechanical stirring obtains mixed solution; The described pollen of surperficial removal of impurities process and the weight ratio of inorganic cobalt salt are (80 ~ 5): 1;
(3) tensio-active agent is added in alkaline solution, add in the mixed solution of step (2) after stirring, stir; Then, at 5 ~ 90 DEG C, drip hydrazine hydrate, stir 0.5 ~ 24 hour; Then obtain solids through Magneto separate, solids, after distillation washing, dehydrated alcohol are washed, is dried and is obtained cobaltosic oxide precursor; By the roasting 1 ~ 8 hour at 200 ~ 290 DEG C of above-mentioned cobaltosic oxide precursor, obtain cobaltosic oxide powder composite particles; By the roasting 2 ~ 6 hours at 300 ~ 500 DEG C of above-mentioned cobaltosic oxide powder composite particles, obtain porous tricobalt tetroxide.
2. porous tricobalt tetroxide is preparing the application in capacitor electrode material; Described porous tricobalt tetroxide is prepared by following methods:
(1) at room temperature, added by pollen in distilled water, stirring, ultrasonic disperse obtain mixture; After said mixture centrifugation, get solids and add in dehydrated alcohol, stir, carry out centrifugal treating after ultrasonic disperse, dry centrifugal after solids, obtain the pollen of surperficial removal of impurities process; Described pollen is porous Pollen Brassicae campestris; Described inorganic cobalt salt is one or more in cobaltous acetate, acetate hydrate cobalt, cobalt chloride, hydrated cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nitric hydrate cobalt, rose vitriol, cobalt sulfate hydrate
(2) pollen getting surperficial removal of impurities process joins in distilled water, then adds inorganic cobalt salt, stirring, ultrasonic vibration; Then add quadrol, mechanical stirring obtains mixed solution; The described pollen of surperficial removal of impurities process and the weight ratio of inorganic cobalt salt are (80 ~ 5): 1;
(3) tensio-active agent is added in alkaline solution, add in the mixed solution of step (2) after stirring, stir; Then, at 5 ~ 90 DEG C, drip hydrazine hydrate, stir 0.5 ~ 24 hour; Then obtain solids through Magneto separate, solids, after distillation washing, dehydrated alcohol are washed, is dried and is obtained cobaltosic oxide precursor; By the roasting 1 ~ 8 hour at 200 ~ 290 DEG C of above-mentioned cobaltosic oxide precursor, obtain cobaltosic oxide powder composite particles; By the roasting 2 ~ 6 hours at 300 ~ 500 DEG C of above-mentioned cobaltosic oxide powder composite particles, obtain porous tricobalt tetroxide.
3. apply according to claims 1 or 2, it is characterized in that: described porous tricobalt tetroxide is elliposoidal, particle diameter is 6 ~ 10 μm, specific surface area 91 ~ 120m
2/ g, surface mesh is of a size of 200 ~ 600nm.
4. apply according to claims 1 or 2, it is characterized in that: in step (1), described pollen is porous Pollen Brassicae campestris; Described inorganic cobalt salt is one or more in cobaltous acetate, acetate hydrate cobalt, cobalt chloride, hydrated cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nitric hydrate cobalt, rose vitriol, cobalt sulfate hydrate.
5. apply according to claims 1 or 2, it is characterized in that: in step (1), the described ultrasonic disperse time is 5 ~ 30 minutes; The mass ratio of pollen and distilled water is 1: (4 ~ 100), and the mass ratio of solids and dehydrated alcohol is 1: (4 ~ 100).
6. apply according to claims 1 or 2, it is characterized in that: in step (2), the pollen of surperficial removal of impurities process and distilled water mass ratio are 1: (5 ~ 20); After adding inorganic cobalt salt, stir 10 ~ 120 minutes, ultrasonic vibration 2 ~ 5 minutes; Then add quadrol, mechanical stirring obtains mixed solution in 10 ~ 30 minutes; The mol ratio of described quadrol and inorganic cobalt salt is 1: (1 ~ 4).
7. apply according to claims 1 or 2, it is characterized in that: in step (3), tensio-active agent is added in alkaline solution, stir and add in the mixed solution of step (2) after 5 ~ 10 minutes, stir 5 ~ 60 minutes; Solids washes 3 ~ 5 times through distillation washing, dehydrated alcohol; Then dry under 40 ~ 60 DEG C of conditions.
8. apply according to claims 1 or 2, it is characterized in that: in step (3), the consumption of described tensio-active agent is 3% ~ 20% of pollen quality; Described alkaline solution is aqueous sodium hydroxide solution or potassium hydroxide aqueous solution; In described alkaline solution, the molar weight of alkali and the molar weight of inorganic cobalt salt are than being (40 ~ 90): 1; The molar weight of described hydrazine hydrate and the molar weight of inorganic cobalt salt are than being (300 ~ 550): 1; Tensio-active agent is PVP, cetyl trimethylammonium bromide or polyoxyethylene glycol.
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| CN106082358A (en) * | 2016-06-22 | 2016-11-09 | 荆门市格林美新材料有限公司 | The preparation method of Cobalto-cobaltic oxide |
| CN106335930A (en) * | 2016-08-16 | 2017-01-18 | 安徽师范大学 | Porous spherical cobaltosic oxide electrode material and preparation method and application thereof |
| CN113044887A (en) * | 2021-03-31 | 2021-06-29 | 辽宁大学 | Cobaltosic oxide porous microsphere, preparation method thereof and application thereof in photo-assisted supercapacitor |
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| CN113044887A (en) * | 2021-03-31 | 2021-06-29 | 辽宁大学 | Cobaltosic oxide porous microsphere, preparation method thereof and application thereof in photo-assisted supercapacitor |
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