CN101607743A - One class has the preparation method of the cobaltates nano-wire array of spinel structure - Google Patents
One class has the preparation method of the cobaltates nano-wire array of spinel structure Download PDFInfo
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- CN101607743A CN101607743A CNA2009100551713A CN200910055171A CN101607743A CN 101607743 A CN101607743 A CN 101607743A CN A2009100551713 A CNA2009100551713 A CN A2009100551713A CN 200910055171 A CN200910055171 A CN 200910055171A CN 101607743 A CN101607743 A CN 101607743A
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Abstract
The invention discloses a kind of is the method that the anti-phase preparation of solid template has the cobaltates nano-wire array of spinel structure with the meso pore silicon oxide material, it is characterized in that at first template being dispersed in the immiscible organic solvent of water in, afterwards, under stirring condition, dropwise add the metal nitrate aqueous solution for preparing in advance in the above-mentioned dispersion system; Behind the uniform mixing, in air, place, make solvent evaporates obtain dried powder; Make to decompose under the confinement effect of metal nitrate in the template duct through roasting again and generate cobaltates with spinel structure; At last, remove the silicon oxide template, the cobaltates nano-wire array that obtains being situated between and see in order and have spinel structure with the sodium hydroxide solution dissolving.The material of preparation has the degree of crystallinity height, the big and equal first-class advantage in aperture of specific surface area, and form adjustable, controllable structure.
Description
Technical field
The present invention relates to a class and be situated between to see in order and have the preparation method of the cobaltates nano-wire array of spinel structure, belong to the synthetic field of inorganic nano material and mesoporous material.
Background technology
But with MCM-41 and SBA-15 be the meso pore silicon oxide material of representative have pore passage structure in order, the physicochemical property of specific surface area and numerous excellences such as pore volume is big, aperture modulation and Heat stability is good, thereby cause people's extensive studies interest.Meanwhile, the research of non-oxide silicon mesoporous material is also constantly being expanded and is being goed deep into.Particularly the transition metal oxide mesoporous material because there is variable chemical state in transition metal, makes it have broad application prospects in fields such as catalysis, sensing, light, electricity, magnetic.
The preparation method of mesoporous material can summarize and be divided into soft template method and hard template method [F.Sch ü th, Angew.Chem.Int.Ed.2003,42,3604.].Soft template method is meant that inorganic precursor (for example: metal alkoxide) at structure directing agent (for example: carry out the method that self-assembly prepares mesoporous material under the effect amphipathic tensio-active agent).At present, adopt soft template method to prepare cerium oxide (CeO
2), zirconium white (ZrO
2), ferric oxide (Fe
2O
3) wait the mesoporous material [F.Sch ü th, Chem.Mater.2001,13,3184.] of transition metal oxide.Yet, because the hydrolysis of metal alkoxide is difficult to control, the synthetic reaction system and the strict control reaction conditions that all needs to adopt complexity of every kind of metal oxide mesoporous material, this has greatly restricted the applied research of metal oxide mesoporous material.By contrast, hard template method adopts constitutionally stable porous silica or porous carbon as the solid template, utilizes host-guest interaction, and metal oxide precursor is introduced the template duct, through the certain post-processing process, remove template at last and obtain the anti-phase metal oxide mesoporous material of structure.Its advantage is that synthetic system is simple, universality good, composition is adjustable, controllable structure and can prepare the metal oxide mesoporous material of height crystallization or even monocrystalline.Therefore, adopt the synthetic non-oxide silicon mesoporous material of hard template method to receive increasing concern.Utilize this method, people successfully prepare the non-oxide silicon mesoporous material [A.-H.Lu, et al., Adv.Mater.2006,18,1793.] that carbon, metal simple-substance, metal oxide, metallic sulfide etc. are formed.But the mesoporous material with cobaltates of spinel structure does not appear in the newspapers as yet.Major cause is that the filling ratio of multi-element metal oxide composition skewness and oxide precursor is not high.Thereby be difficult to obtain the cobaltates nano-wire array that phase purity height, specific surface area are big, be situated between and see in order and have spinel structure.
Summary of the invention
The objective of the invention is to adopt mesopore silicon oxide is cobaltates (comprising cobalt acid copper, cobalt acid manganese and the cobalt acid nickel) nano-wire array that the anti-phase preparation of solid template is situated between and sees in order and have spinel structure.Institute's synthetic material has the big and equal first-class advantage in aperture of degree of crystallinity height, specific surface area and pore volume.
The preparation method of the cobaltates nano-wire array that the present invention proposes with spinel structure, at first the mesopore silicon oxide template is dispersed in the water-fast organic solvent, afterwards, under the situation of vigorous stirring, dropwise add the metal nitrate aqueous solution for preparing in advance in the above-mentioned dispersion system; After mixing, in air, place, make solvent evaporates obtain dried powder; Make to decompose under the confinement effect of metal nitrate in the template duct through roasting again and generate cobaltates with spinel structure; At last, remove the silicon oxide template, the cobaltates nano-wire array that obtains being situated between and see in order and have spinel structure with the sodium hydroxide solution dissolving.
Among the present invention, can be mesopore silicon oxide SBA-15[D.Zhao with two-dimentional hexagonal structure as the material of template, et al., Science 1998,279, and 548.], also can be KIT-6[F.Kleitz with cubic structure, et al., Chem.Commun.2003,2136.], SBA-16[D.Zhao, et al., J.Am.Chem.Soc.1998,120,6024.], FDU-12[J.Fan, et al., mesopore silicon oxide such as Angew.Chem.Int.Ed.2006,42,3146.]; The aqueous solution of metal nitrate is as presoma, and Cu, Mn or Ni, Co ionic mol ratio are between 0.1-0.8 in cupric nitrate (or manganous nitrate, nickelous nitrate) and the Xiao Suangu; Organic solvent adopts normal hexane, and other and the immiscible solvent of water as tetrahydrofuran (THF), also can be obtained similar effect.
Among the present invention, be that the concrete steps of the cobaltates nano-wire array of template preparation with spinel structure are as follows with the mesopore silicon oxide:
1. the uniform mixing of mesopore silicon oxide template and metal nitrate precursor solution: mesopore silicon oxide template homodisperse in normal hexane, the mass ratio of silicon oxide and normal hexane is 1: 10-1: 50, the metal nitrate aqueous solution for preparing by certain mol proportion dropwise adds in the above-mentioned dispersion system under the situation of vigorous stirring, the volume that adds is suitable with the pore volume of template, magnetic agitation 1-3 hour, temperature was envrionment temperature 5-35 ℃;
2. the volatilization of organic solvent: solution places open container, and temperature is envrionment temperature 5-35 ℃;
3. roasting: the mixture that step 2 obtains was finished the decomposition of metal nitrate and the crystallization of metal oxide at 350-450 ℃ of roasting 4-6 hour;
4. the removal of silicon oxide template: it is that the aqueous sodium hydroxide solution of 1-2M stirred 12-48 hour at 30-80 ℃ that the mixture that step 3 obtains places concentration, make the dissolving of silicon oxide template, again through centrifugal, cleaning and dry, finally, obtain anti-phase and have a cobaltates nano-wire array of spinel structure with the template meso-hole structure.
Jie that the present invention obtains sees in order and cobaltates nano-wire array material with spinel structure comprises cobalt acid copper, cobalt acid manganese and cobalt acid nickel.
Among the present invention, the material that obtains has polycrystallinity.
Among the present invention, material has verily duplicated the topological framework of mesopore silicon oxide template, has big specific surface area (90-130m
2g
-1) and pore volume (0.30-0.45cm
3g
-1), most probable aperture 4.5-6.0nm.The diameter of nano wire can be regulated in the scope of 6-8nm according to the size of pore size of template, and length is 100-200nm.
The present invention synthesizes a series of cobaltates nano-wire arrays with spinel structure first.They have the degree of crystallinity height, and specific surface area is big, the equal first-class advantage in aperture, and form adjustable, controllable structure, thereby can be used as catalyzer, transmitter, electrode materials and obtain widely at petrochemical complex, electronic information and high-technology field and use.
Description of drawings
Fig. 1 is wide-angle x-ray diffraction (XRD) figure by the cobalt acid copper nano-wire array with spinel structure of embodiment 1 prepared; Illustration is corresponding selected area electron diffraction (SAED) style.
Fig. 2 is transmission electron microscope (TEM) photo of pressing the cobalt acid copper nano-wire array of embodiment 1 prepared.
Fig. 3 is the wide-angle XRD figure by the cobalt acid manganese nano-wire array with spinel structure of embodiment 2 prepared; Illustration is corresponding SAED style.
Fig. 4 is a TEM photo of pressing the cobalt acid manganese nano-wire array of embodiment 2 prepared.
Fig. 5 is the wide-angle XRD figure by the cobalt acid nickel nano-wire array with spinel structure of embodiment 3 prepared; Illustration is corresponding SAED style.
Fig. 6 is a TEM photo of pressing the cobalt acid nickel nano-wire array of embodiment 3 prepared.
Fig. 7 is the wide-angle XRD figure by the cobalt acid copper nano-wire network with spinel structure of embodiment 4 prepared; Illustration is corresponding SAED style.
Fig. 8 is a TEM photo of pressing the cobalt acid copper nano-wire network of embodiment 4 prepared.
Embodiment
Further set forth content of the present invention below in conjunction with embodiment, but protection scope of the present invention is not limited in embodiment.
Embodiment 1
Cobalt acid copper nano-wire array synthetic with spinel structure: at first, with Gerhardite (Cu (NO)
23H
2O) with Cobaltous nitrate hexahydrate (Co (NO)
26H
2O) mol ratio with 1: 2 (Cu/Co) is mixed with the about 1g ml of concentration
-1The aqueous solution.The baked mesopore silicon oxide SBA-15 of 0.5g is dispersed in the 20ml normal hexane, stirred under the room temperature 3 hours, get the metal nitrate aqueous solution that 0.5ml prepares then and under the situation of vigorous stirring, dropwise add wherein; Stir and made solvent evaporates obtain dried powder in 12-24 hour; This matrix material is placed retort furnace, metal nitrate is decomposed generate cobalt acid copper (CuCo with spinel structure
2O
4); At last, silicon oxide template 20ml 2M sodium hydroxide (NaOH) aqueous solution, stirring at room was removed in 24 hours.The centrifugation product, and washing is dry, obtains the cobalt acid copper nano-wire array with spinel structure of crystallization.
The wide-angle x-ray diffraction pattern (Fig. 1) of product shows that the cobalt acid copper of generation is the pure phase of spinel structure.Product selected area electron diffraction style (Fig. 1 illustration) is the stack of diffraction spot and diffraction ring, shows that the cobalt acid copper of generation has polycrystallinity.The transmission electron microscope photo of product as shown in Figure 2, the cobalt acid copper nano-wire with spinel structure is situated between to see and is ordered arrangement, the diameter 7-8nm of single nano-wire, length 100-200nm.The texture parameter of product comprises that BET specific surface area, pore volume and BJH most probable aperture list in table 1.
Embodiment 2
Cobalt acid manganese nano-wire array synthetic with spinel structure: at first, with manganese nitrate aqueous solution (Mn (NO)
2, 50wt%) with Cobaltous nitrate hexahydrate (Co (NO)
26H
2O) mol ratio with 1: 2 (Mn/Co) is mixed with the about 1g ml of concentration
-1The aqueous solution.The baked mesopore silicon oxide SBA-15 of 0.5g is dispersed in the 20ml normal hexane, stirred under the room temperature 3 hours, get the metal nitrate aqueous solution that 0.5ml prepares then and under the situation of vigorous stirring, dropwise add wherein; Stir and made solvent evaporates obtain dried powder in 12-24 hour; This matrix material is placed retort furnace, metal nitrate is decomposed generate cobalt acid manganese (MnCo with spinel structure
2O
4); At last, silicon oxide template 20ml 2M sodium hydroxide (NaOH) aqueous solution, stirring at room was removed in 24 hours.The centrifugation product, and washing is dry, obtains the cobalt acid manganese nano-wire array with spinel structure of crystallization.
The wide-angle x-ray diffraction (XRD) of product and selected area electron diffraction (SAED) style are shown in Fig. 3 and illustration.The transmission electron microscope photo of product as shown in Figure 4.The texture parameter of product sees Table 1.
Embodiment 3
Cobalt acid nickel nano-wire array synthetic with spinel structure: at first, with Nickelous nitrate hexahydrate (Ni (NO)
26H
2O) with Cobaltous nitrate hexahydrate (Co (NO)
26H
2O) mol ratio with 1: 2 (Ni/Co) is mixed with the about 1g ml of concentration
-1The aqueous solution.The baked mesopore silicon oxide SBA-15 of 0.5g is dispersed in the 20ml normal hexane, stirred under the room temperature 3 hours, get the metal nitrate aqueous solution that 0.5ml prepares then and under the situation of vigorous stirring, dropwise add wherein; Stir and made solvent evaporates obtain dried powder in 12-24 hour; This matrix material is placed retort furnace, metal nitrate is decomposed generate cobalt acid nickel (NiCo with spinel structure
2O
4); At last, silicon oxide template 20ml 2M sodium hydroxide (NaOH) aqueous solution, stirring at room was removed in 24 hours.The centrifugation product, and washing is dry, obtains the cobalt acid nickel nano-wire array with spinel structure of crystallization.
The wide-angle x-ray diffraction (XRD) of product and selected area electron diffraction (SAED) style are shown in Fig. 5 and illustration.The transmission electron microscope photo of product as shown in Figure 6.The texture parameter of product sees Table 1.
Table 1
Embodiment 4
The mesopore silicon oxide template is not limited only to the SBA-15 of two-dimentional hexagonal structure, other mesopore silicon oxide, for example, cube KIT-6 form interts by two cover foraminous spiral tracts in the hole system, and SBA-16 that arrange according to body-centered cubic and face-centered cubic respectively in cage shape hole and FDU-12 etc. can be as the nanostructures of the synthetic cobaltates of template duplicating.By selecting different silicon oxide templates can realize the regulation and control of cobaltates nano-wire array structure.Present embodiment will adopt the network structure of KIT-6 as the synthetic cobalt acid of template duplicating copper nano-wire, further specify this preparation method's versatility and diversity.
Cobalt acid copper nano-wire network synthetic with spinel structure: at first, with Gerhardite (Cu (NO)
23H
2O) with Cobaltous nitrate hexahydrate (Co (NO)
26H
2O) mol ratio with 1: 2 (Cu/Co) is mixed with the about 1g ml of concentration
-1The aqueous solution.The baked mesopore silicon oxide KIT-6 of 0.5g is dispersed in the 20ml normal hexane, stirred under the room temperature 3 hours, get the metal nitrate aqueous solution that 0.5ml prepares then and under the situation of vigorous stirring, dropwise add wherein; Stir and made solvent evaporates obtain dried powder in 12-24 hour; This matrix material is placed retort furnace, metal nitrate is decomposed generate cobalt acid copper (CuCo with spinel structure
2O
4); At last, silicon oxide template 20ml 2M sodium hydroxide (NaOH) aqueous solution, stirring at room was removed in 24 hours.The centrifugation product, and washing is dry, obtains the cobalt acid copper nano-wire network with spinel structure of crystallization.
The wide-angle x-ray diffraction (Fig. 7) of product shows that the cobalt acid copper of generation is the pure phase of spinel structure.Product selected area electron diffraction (Fig. 7 illustration) is the stack of diffraction spot and diffraction ring, shows that the cobalt acid copper of generation has polycrystallinity.The transmission electron microscope photo of product as shown in Figure 8, the cobalt acid copper nano-wire network Jie view hole with spinel structure is arranged in order, the diameter of nano wire is limited by pore size of template, is about 7-8nm, the meso-hole structure particle size is between 50-150nm.The BET specific surface area of product, pore volume and BJH most probable aperture are respectively 94m
2g
-1, 0.33cm
3g
-1And 4.9nm.
Claims (6)
1. a class has the preparation method of the cobaltates nano-wire array of spinel structure, it is characterized in that at first the mesopore silicon oxide template being dispersed in the immiscible organic solvent of water in, afterwards, the metal nitrate aqueous solution as presoma with preparation in advance dropwise adds in the above-mentioned dispersion system under stirring condition; After mixing, be placed in the air, make solvent evaporates obtain dried powder; Make to decompose under the confinement effect of metal nitrate in the template duct through roasting again and generate cobaltates with spinel structure; At last, remove the silicon oxide template, the cobaltates nano-wire array that obtains being situated between and see in order and have spinel structure with the sodium hydroxide solution dissolving; The mesopore silicon oxide template that is adopted is KIT-6, SBA-16, the FDU-12 mesopore silicon oxide that has the SBA-15 of two-dimentional hexagonal structure or have cubic structure; Described organic solvent is and immiscible normal hexane of water or tetrahydrofuran (THF).
2. preparation method according to claim 1, concrete synthesis step is as follows:
(1). the uniform mixing of mesopore silicon oxide template and metal nitrate precursor solution: mesopore silicon oxide template homodisperse in organic solvent, the mass ratio of silicon oxide and the immiscible organic solvent of water is 1: 10-1: 50, by Cu, Mn or Ni and Co ionic mol ratio is the metal nitrate aqueous solution between the 0.1-0.8, under stirring condition, dropwise add in the above-mentioned dispersion system, the volume that adds is suitable with the pore volume of template, stirs at 5-35 ℃ of envrionment temperature lower magnetic force;
(2). the volatilization of organic solvent: under envrionment temperature 5-35 ℃ condition, solution is placed open container;
(3). roasting: the mixture that step (2) is obtained is finished the decomposition of metal nitrate and the crystallization of metal oxide 350-450 ℃ of roasting;
(4). the removal of silicon oxide template: the mixture that step (3) is obtained places the aqueous solution of sodium hydroxide, 30-80 ℃ of stirring, make the dissolving of silicon oxide template, again through centrifugal, cleaning and dry, finally, obtain anti-phase and have a cobaltates nano-wire array of spinel structure with the template meso-hole structure.
3. preparation method according to claim 1 and 2 is characterized in that as the nitrate in the metal nitrate aqueous solution of presoma be Cobaltous nitrate hexahydrate, Gerhardite, manganese nitrate aqueous solution, Nickelous nitrate hexahydrate, cupric nitrate or nickelous nitrate.
4. preparation method according to claim 2 is characterized in that:
(a) the described magnetic agitation time of step (1) is 1-3 hour;
(b) time of the described roasting of step (3) is 4-6 hour;
(c) the described aqueous sodium hydroxide solution concentration of step (4) is 1-2M, and churning time is 12-48 hour.
5. preparation method according to claim 1, it is characterized in that it is that the nano wire Jie sight with cobalt acid copper, cobalt acid manganese or the sour nickel nano-wire array of cobalt of spinel structure is ordered arrangement that prepared Jie sees Ordered Materials, the diameter of single nano-wire is regulated in the scope of 6-8nm, and length is 100-200nm.
6. preparation method according to claim 1 and 2 is characterized in that the specific surface area 90-130m of prepared nano-wire array
2g
-1, pore volume 0.30-0.45cm
3g
-1, most probable aperture 4.5-6.0nm.
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| CN104437538A (en) * | 2014-12-02 | 2015-03-25 | 南开大学 | Preparation method of low-temperature high-efficiency denitration catalyst-MnCo2O4 |
| CN104659358A (en) * | 2015-01-30 | 2015-05-27 | 南京工业大学 | Preparation method of hollow nickel cobaltate nano polyhedron |
| CN104659358B (en) * | 2015-01-30 | 2017-02-22 | 南京工业大学 | Preparation method of hollow nickel cobaltate nano polyhedron |
| CN104787809A (en) * | 2015-04-16 | 2015-07-22 | 电子科技大学 | Preparation method for nickel cobaltite material adopting rattan-shaped three-dimensional nano-structure |
| WO2019109831A1 (en) * | 2017-12-05 | 2019-06-13 | 惠州学院 | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen |
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| CN109772334A (en) * | 2018-12-28 | 2019-05-21 | 宁夏大学 | A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof |
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| CN110606747B (en) * | 2019-10-16 | 2021-09-07 | 西北工业大学 | Preparation method of isotropic ceramic nanowire preform |
| CN111129454A (en) * | 2019-12-17 | 2020-05-08 | 上海工程技术大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN114620763A (en) * | 2021-11-26 | 2022-06-14 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous copper gallate gas-sensitive material and preparation method thereof |
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Application publication date: 20091223 |