CN102092797B - Sol-gel preparation method of porous nickel cobaltate material - Google Patents
Sol-gel preparation method of porous nickel cobaltate material Download PDFInfo
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- CN102092797B CN102092797B CN2011100334973A CN201110033497A CN102092797B CN 102092797 B CN102092797 B CN 102092797B CN 2011100334973 A CN2011100334973 A CN 2011100334973A CN 201110033497 A CN201110033497 A CN 201110033497A CN 102092797 B CN102092797 B CN 102092797B
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Abstract
The invention discloses a sol-gel preparation method of a porous nickel cobaltate material. The method comprises the following steps of: dissolving cobalt acetate and nickel acetate in distilled water to obtain acetate aqueous solution, adding citric acid aqueous solution, uniformly mixing, adding distilled water for diluting until the concentration of the cobalt acetate is between 0.016 and 0.05 mol/L to obtain diluted solution, and drying to obtain a precursor; and grinding and calcining the precursor to obtain the porous nickel cobaltate material. The method has a simple preparation process and is environmentally-friendly; and the obtained nickel cobaltate has a spinel cubic phase, high purity, high degree of crystallinity, uniform pore diameter distribution and the pore diameter size of less than 200 nanometers, and is porous.
Description
One, technical field
The present invention relates to a kind of preparation method of inorganic porous material, specifically a kind of sol-gel process for preparing of porous cobalt acid nickel material.
Two, background technology
NiCo
2O
4Be a kind of composite oxides of spinel type, the cobalt acid nickel of discovering in recent years has good application in many aspects, is a kind of important inorganic functional material.For example, cobalt acid nickel is good electrode materials in alkaline electrolyte, can be used as the active electrode of electrochemical capacitor, and some material is shown good catalytic activity.Someone finds NiCo
2O
4To H
2O
2Electrochemical reduction has high catalytic activity and stability, in petroleum industry to the advantages of high catalytic activity of having separated out of oxygen.Cobalt acid nickel also shows good magnetic performance after deliberation.
Do not appear in the newspapers less than the sour nickel material of porous cobalt of 200nm in the aperture of at present for preparing method's research of cobalt acid nickel also seldom, preparing even structure.The method that forefathers prepare cobalt acid nickel material mainly contains high temperature solid-state method, hydrothermal method, sol-gel method etc.The temperature that high temperature solid state reaction is had relatively high expectations can cause size distribution inhomogeneous usually, and is dispersed bad.For hydrothermal method, reaction needs is carried out under comparatively high temps and pressure, has relatively high expectations for reaction conditions and equipment material, is difficult to industriallization and enlarges production.And sol-gel method has overcome the shortcoming and defect of above-mentioned several method to a certain extent, can under comparatively gentle condition, realize a large amount of synthetic of material, has become one of important means of current preparation material.Prepare in the sol-gel method of cobalt acid nickel forefathers, most methods are with the part of macromolecule organic as metals ion, with organism as solvent, but macromolecule organic costs an arm and a leg, not environmental protection and much organism is harmful.Therefore the method that we hope to find that a kind of technology is simple, cost of material cheap, environmental protection and harmless collosol and gel prepare cobalt acid nickel.
Three, summary of the invention
The present invention is the weak point for fear of above-mentioned prior art, provides that a kind of controllability is good, phase purity is high, the sol-gel process for preparing of the porous cobalt acid nickel material of even structure.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention are to operate according to the following steps:
A, Cobaltous diacetate and nickel acetate are dissolved in zero(ppm) water, are made into acetate aqueous solution, make that the concentration of Cobaltous diacetate is 0.16-0.5mol/L in the said acetate aqueous solution, the mol ratio of said Cobaltous diacetate and said nickel acetate addition is 2: 1;
B, Hydrocerol A is dissolved in the zero(ppm) water; Be made into aqueous citric acid solution; With getting mixing solutions in the said aqueous citric acid solution adding step a gained acetate aqueous solution, the mole number sum of said Cobaltous diacetate and nickel acetate is 1-2 with the ratio of the mole number of said Hydrocerol A: 1 then;
C, adding distil water dilution in said mixing solutions make that the concentration of Cobaltous diacetate is 0.016-0.05mol/L in the said mixing solutions, diluting soln; Said diluting soln was got precursor in 120-130 ℃ of dry 12-16 hour;
D, 200 mesh sieves are pulverized and crossed to said precursor, promptly get the sour nickel material of porous cobalt in 2-3 hour 350-400 ℃ of calcining then.
The characteristics of the sol-gel process for preparing of porous cobalt of the present invention acid nickel material also are: adding distil water dilution in said mixing solutions among the said step c makes that the volumetric molar concentration of Cobaltous diacetate is 0.016-0.03mol/L in the said mixing solutions.
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention also are: the mole number sum that Cobaltous diacetate and nickel acetate described in the said step b add is 1: 1 with the ratio of the mole number that said Hydrocerol A adds.
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention also are: calcining temperature is 380-400 ℃ in the said steps d, and calcination time is 2.5-3 hour.
What the present invention adopted is the metal-chelating gel method, and gained cobalt acid nickel is spinel type, and be characterized in: the vesicular of even structure, the aperture is less than 200nm.
Compared with present technology beneficial effect of the present invention is embodied in:
1, the present invention adopts the synthesizing porous cobalt of sol-gel method acid nickel material, compare with other chemical synthesis process have environmental protection, advantages such as technology is simple, no waste water and dregs, low-temp low-pressure.
2, gained cobalt of the present invention acid nickel material is a spinel type cube phase, purity is high, percent crystallinity is high, porous, even aperture distribution and aperture size be less than 200nm.Because the pattern of material is uniform vesicular, have that volume density is little, specific surface area big, than characteristics such as mechanics performance height, be a kind of novel structure function material, can be used for catalytic reaction engineering, electrochemistry and field of petrochemical industry.
Four, description of drawings
Fig. 1 is the XRD figure of the porous cobalt acid nickel material of embodiment of the invention 1-5 preparation.Wherein curve 1 is the XRD curve of the porous cobalt acid nickel material of embodiment 1 preparation; Curve 2 is the XRD curve of the porous cobalt acid nickel material of embodiment 2 preparations; Curve 3 is the XRD curve of the porous cobalt acid nickel material of embodiment 3 preparations; Curve 4 is the XRD curve of the porous cobalt acid nickel material of embodiment 4 preparations; Curve 5 is the XRD curve of the porous cobalt acid nickel material of embodiment 5 preparations.
Fig. 2 is ESEM (SEM) photo of the porous cobalt acid nickel material of the embodiment of the invention 1 preparation.
Five, embodiment
For better understanding the present invention, below in conjunction with accompanying drawing and instance the present invention is further specified, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix; Be made into acetate aqueous solution; In acetate aqueous solution, adding 50mL concentration then is the aqueous citric acid solution of 0.48mol/L, and to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.016mol/L in the adding distil water dilution again, mixes to be placed in the loft drier; Got presoma down in dry 16 hours at 120 ℃; The gained precursor is ground and cross 200 mesh sieves, be placed in the tube furnace, promptly get the sour nickel material of porous cobalt in 400 ℃ of calcining 2h.
Embodiment 2:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix; Be made into acetate aqueous solution; In acetate aqueous solution, adding 50mL concentration then is the aqueous citric acid solution of 0.48mol/L, and to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.016mol/L in the adding distil water dilution again, mixes to be placed in the loft drier; Got presoma down in dry 12 hours at 130 ℃; The gained precursor is ground and cross 200 mesh sieves, be placed in the tube furnace, promptly get the sour nickel material of porous cobalt in 350 ℃ of calcining 3h.
Embodiment 3:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix; Be made into acetate aqueous solution; In acetate aqueous solution, adding 50mL concentration then is the aqueous citric acid solution of 0.48mol/L, and to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.03mol/L in the adding distil water dilution again, mixes to be placed in the loft drier; Got presoma down in dry 14 hours at 125 ℃; The gained precursor is ground and cross 200 mesh sieves, be placed in the tube furnace, promptly get the sour nickel material of porous cobalt in 380 ℃ of calcining 2h.
Embodiment 4:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 1.0mol/L and nickel acetate solution that 50mL concentration is 0.5mol/L mix; Be made into acetate aqueous solution; In acetate aqueous solution, adding 50mL concentration then is the aqueous citric acid solution of 1.5mol/L, and to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.05mol/L in the adding distil water dilution again, mixes to be placed in the loft drier; Got presoma down in dry 16 hours at 120 ℃; The gained precursor is ground and cross 200 mesh sieves, be placed in the tube furnace, promptly get the sour nickel material of porous cobalt in 400 ℃ of calcining 2h.
Embodiment 5:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 1.0mol/L and nickel acetate solution that 50mL concentration is 0.5mol/L mix; Be made into acetate aqueous solution; In acetate aqueous solution, adding 50mL concentration then is the aqueous citric acid solution of 0.75mol/L, and to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.04mol/L in the adding distil water dilution again, mixes to be placed in the loft drier; Got presoma down in dry 12 hours at 130 ℃; The gained precursor is ground and cross 200 mesh sieves, be placed in the tube furnace, promptly get the sour nickel material of porous cobalt in 400 ℃ of calcining 2h.
The XRD test result of the porous cobalt acid nickel material of embodiment 1-5 preparation is seen curve 1-5 among Fig. 1, and as can beappreciated from fig. 1 all diffraction peaks can both be corresponding with the base peak of the spinel type of bottom, and hence one can see that, and gained cobalt acid nickel is a cube phase spinel structure.
The SEM test result of the porous cobalt acid nickel material of embodiment 1 preparation is seen Fig. 2, and material is amplified 10000 times, and we can see the surface tissue of material clearly.It is characterized in that: even structure, porous, the aperture is less than 200nm.Because the pattern of material is uniform vesicular, have that volume density is little, specific surface area big, than characteristics such as mechanics performance height, be a kind of novel structure function material, can be used for catalytic reaction engineering, electrochemistry and field of petrochemical industry.
Claims (4)
1. the sol-gel process for preparing of porous cobalt acid nickel material is characterized in that operating according to the following steps:
A, Cobaltous diacetate and nickel acetate are dissolved in zero(ppm) water, are made into acetate aqueous solution, make that the concentration of Cobaltous diacetate is 0.16-0.5mol/L in the said acetate aqueous solution, the mol ratio of said Cobaltous diacetate and said nickel acetate addition is 2: 1;
B, Hydrocerol A is dissolved in the zero(ppm) water; Be made into aqueous citric acid solution; With getting mixing solutions in the said aqueous citric acid solution adding step a gained acetate aqueous solution, the mole number sum of said Cobaltous diacetate and nickel acetate is 1-2 with the ratio of the mole number of said Hydrocerol A: 1 then;
C, adding distil water dilution in said mixing solutions make that the concentration of Cobaltous diacetate is 0.016-0.05mol/L in the said mixing solutions, diluting soln; Said diluting soln was got presoma in 120-130 ℃ of dry 12-16 hour;
D, 200 mesh sieves are pulverized and crossed to said presoma, promptly get the sour nickel material of porous cobalt in 2-3 hour 350-400 ℃ of calcining then.
2. the sol-gel process for preparing of porous cobalt according to claim 1 acid nickel material is characterized in that: adding distil water dilution in said mixing solutions among the said step c makes that the volumetric molar concentration of Cobaltous diacetate is 0.016-0.03mol/L in the said mixing solutions.
3. the sol-gel process for preparing of porous cobalt acid nickel material according to claim 1 is characterized in that: the mole number sum that Cobaltous diacetate and nickel acetate described in the said step b add is 1: 1 with the ratio of the mole number that said Hydrocerol A adds.
4. the sol-gel process for preparing of porous cobalt acid nickel material according to claim 1, it is characterized in that: calcining temperature is 380-400 ℃ in the said steps d, calcination time is 2.5-3 hour.
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| CN102350504A (en) * | 2011-10-27 | 2012-02-15 | 哈尔滨工业大学 | Preparation method of Fe2Ni alloy powder in nitric acid system |
| CN104870087A (en) * | 2012-11-09 | 2015-08-26 | 巴斯夫欧洲公司 | Process for producing a carbon-supported nickel-cobalt-oxide catalyst and its use in rechargeable electrochemical metal-oxygen cells |
| CN103400998B (en) * | 2013-07-22 | 2015-11-18 | 烟台大学 | A kind of electrochemistry assisting sol gel method prepares the method for γ-cobalt acid sodium electrode material |
| CN104022261A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of composite oxide AB2O4 for lithium ion secondary battery cathode material |
| CN105399149B (en) * | 2015-11-24 | 2017-09-29 | 张铭朔 | A kind of preparation method of electrode material for super capacitor |
| CN107473273A (en) * | 2017-08-02 | 2017-12-15 | 东北大学秦皇岛分校 | Three-dimensional structure micron order cobalt acid Ni cluster, preparation method and the usage |
| CN107324407B (en) * | 2017-08-15 | 2019-12-10 | 陕西科技大学 | NiCo 2 O 4 hexagonal column crystal and preparation method thereof |
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| CN101254952A (en) * | 2008-04-02 | 2008-09-03 | 钢铁研究总院 | Acetate doping natrium cobaltite thermoelectric materials and preparation method thereof |
| CN101549890A (en) * | 2009-04-30 | 2009-10-07 | 中山大学 | Solvothermal synthesis method of nickel cobaltate nano particles |
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| CN101254952A (en) * | 2008-04-02 | 2008-09-03 | 钢铁研究总院 | Acetate doping natrium cobaltite thermoelectric materials and preparation method thereof |
| CN101549890A (en) * | 2009-04-30 | 2009-10-07 | 中山大学 | Solvothermal synthesis method of nickel cobaltate nano particles |
Non-Patent Citations (2)
| Title |
|---|
| Jian Liu et al..STUDY OF THE CATALYTIC COMBUSTION OF DIESEL SOOT OVER NANOMETRIC LANTHANUM-COBALT MIXED OXIDE CATALYSTS.《React.Kinet.Catal.Lett.》.2006,第87卷(第1期),107-114. * |
| 韩景立等.新柠檬酸溶胶凝胶法研究.《电源技术》.2001,第25卷(第3期), * |
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