CN103831443A - Method for utilizing controllability of ionic liquid water interface to prepare cobalt/cobalt oxide nanofilm - Google Patents
Method for utilizing controllability of ionic liquid water interface to prepare cobalt/cobalt oxide nanofilm Download PDFInfo
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Abstract
Disclosed is a method for utilizing controllability of an ionic liquid water interface to prepare a cobalt/cobalt oxide nanofilm. The method includes that KBH4 is utilized as a reducing agent, a transition metal cobalt/cobalt oxide nanofilm structure material is realized on the insoluble ionic liquid water interface, and water-insoluble imidazolyl cations and weak-coordination composite anions like PF-6 are selected for ionic liquid; infrared spectrometry is performed on pure ionic liquid, supernate, liquid cobalt/cobalt oxide colloid and centrifugally-dried solid, and preparation of a completely-clean cobalt/cobalt oxide nanofilm is realized if the ionic liquid is not adsorbed on the surface of cobalt/cobalt oxide before and after centrifugation. By the method, control on nanofilm structure can be realized by changing substituent groups on an imidazole ring and cations. Preparation of a clean and controllable cobalt/cobalt oxide nanofilm is realized on the ionic liquid water interface on the basis of selective weak adsorption effect and template effect of the ionic liquid on the metal surface.
Description
Technical field
The present invention relates to technical field of nano material, particularly a kind of controlled method of preparing cobalt/cobalt oxide nanometer film of ionic liquid water termination of utilizing.
Background technology
Nano structural material, because of its unique physical and chemical performance, is showing potential application prospect aspect scientific research and commercial Application, realize the controlled and continuity of nano structural material prepare the study hotspot that is still every field by suitable design.Cobalt output 80% for the production of various alloys, they have reasonable character at magnetic, hardness, the aspect such as heat-resisting, wear-resistant and anticorrosive; Artificial radioisotope's Co 60 can replace X ray, is also used for treating cancer; Cobalt compound is for medicine, pigment, drier, catalyst and ceramic glaze etc., as Cobastab
12it is exactly a kind of cobalt compounds.Metallic cobalt is important electrode material in electrochemical research, is widely used in the research of the aspects such as plating, chemical energy source and electro-catalysis.Carry out the research of various adsorbing species behaviors on metallic cobalt surface, the understanding and cognition tool of catalytic mechanism, electrode interface process etc. is of great significance.If Co and Co base alloy and oxide are by extensively as magnetic material and catalyst.
Nano thin-film can be divided into two classes: (1) is made up of the film of (or pile up form) nano particle; (2) between nano particle, there are more space or unordered atom or another kind of material, i.e. nano compound film.The preparation of nano thin-film is broadly divided into physical method and the large class of chemical method two.The technology such as that physical method mainly adopts is optical, electrical, magnetic, power are evaporated material in vacuum or inert atmosphere, form the ultrafine dust of nanoscale, then on substrate, assemble film forming, and Physical mainly contains vacuum evaporation, sputter and ion plating method etc.Adopt physical method can realize the preparation of various metals and alloy nano film, as utilize sputtering method can obtain multiple nano metal, comprise the refractory metal of the more difficult realization of conventional evaporation, and can obtain many group members' compound nano particulate.But physical method generally need to carry out under special appointed condition, and preparation condition requires harsh.Chemical method is different from Physical and mainly in preparation, is attended by chemical reaction, and chemical method mainly contains electrochemistry synthetic (electro-deposition and electrochemical redox), self-assembling technique, vapor deposition method, chemical precipitation method, hydrothermal synthesis method and sol-gal process etc.Wherein liquid phase reduction and electrochemical deposition technique are to realize the method that metal nano material is conventional.Electrochemical deposition method utilizes electrochemical method metallic atom to be deposited to the nano structure membrane that forms different-shape in conductive substrates, by changing electro-deposition techniques, plating solution composition, sedimentary condition etc. are controlled structure and the size of roughness of film, thickness and nano particle, but electrodeposited nanocrystalline film depends on substrate, film can not independently form.And liquid phase oxidation reducing process (as polyalcohol method, template synthetic method etc.) is the synthetic the most frequently used method of metal nano material; under liquid-phase condition, (in the aqueous solution or organic solution) is by selecting suitable protective agent and reducing agent to realize the preparation of metal nano material; and can realize by template (as soft template micro emulsion structure or porous alumina formwork etc.) control of various metals nanostructured, and liquid phase reduction has that equipment is simple, easy to operate, adjustability and diversity, be easy to the features such as industrialization and have broad prospects.Although liquid phase method is widely used at aspects such as preparation nanostructureds (as 0 dimension nano particle and 1-dimention nano pipe/line), but the control research to two-dimensional nano film is less, and under liquid-phase condition in the preparation process of metal nano material, often to add single protective agent or kinds of protect agent to keep the stable existence of metal Nano structure, protective agent is adsorbed on metal nanoparticle surface and stops its reunion, the normal macromolecular structure with backbone that adopts of protective agent, can cause on the one hand the pollution of environment, protective agent can cause metal nano material in the process of washing to lose serious in the absorption on metal nanoparticle surface on the other hand, wash insufficient.Obtain controlled, the stable and high nano structural material of productive rate of surface cleaning, structure, must be optimized combination to existing synthetic method, should strive to find some new methods simultaneously.
In the last few years, ionic liquid at room temperature is because of its unique performance, as high polarization characteristic (RTIL), insignificant vapour pressure, wide electrochemical window and good heat endurance are used as " green solvent " and are widely used in the preparation of nano structural material.In the preparation of metal and alloy nano structural material, ionic liquid is as solvent or protective agent, and suitable adjusting synthetic method and by suitable post processing can realize the preparation of nano metal and alloyed oxide material.
Ionic liquid can be made metal nano material stable existence or stop it to reunite in the absorption of metal surface by its zwitterion, wherein the absorption property formation electrostatic protection layer of ionic liquid by surface of metal particles or realize the stable existence of metal nano ion by " bulk effect " of adion.Simultaneously ionic liquid is playing an important role aspect surface characteristic, particle diameter and the structure control of nanometer result material as surfactant and structure directing agent because of its good solubility property and ionization function.Ionic liquid can directly be realized the controlled preparation of nano structural material as solvent or adjuvant in conjunction with traditional synthetic method.The people such as Yu synthesized water miscible and stable Ni nano particle and to its optionally Catalytic Hydrogenation Properties measure, result shows good catalytic activity.Utilize the weak characterization of adsorption of ionic liquid in surface of metal particles; can realize " cleaning " preparation of metal nanoparticle; as utilize ionic liquid to synthesize the nanometer Pd/C catalyst of high dispersive as protective agent; because of the interaction a little less than its ionic liquid and Pd particle; the ionic liquid of Pd particle surface absorption easily cleans, and result shows that the synthetic Pd/C catalyst of the method shows the Electrocatalytic Oxidation of Methanol activity (1.6 times) strengthening than traditional organic protective agent.Meanwhile, can realize the preparation of alloy nanoparticle at ion liquid system, as CoPt etc.In research surface ion liquid system, there are nano-micelle and other oriented structures.
The more important thing is, the functional group containing N structure is found in recent research, as alkyl ammonia or amido etc., particularly with the anion of compound weak coordination, as BF
4 -, PF
6 -deng the ionic liquid forming and the interaction of metal surface atom than carbonyl or sulfur-bearing group a little less than, mean and utilize these groups can realize the metal nanoparticle that high-quality " cleans " and empty G&W is stable.Wherein, glyoxaline ion liquid receives much concern as the difunctional character of solvent and stabilizing agent simultaneously in the preparation of metal nano material, the particularly oriented structure phase of glyoxaline ion liquid height, as pi-pi accumulation structure between the Supramolecular Network structure forming by hydrogen bond and imidazole ring, affect the controlled preparation of metal nano particle diameter and structure.Contrast existing chemical method and prepare the routine techniques of film, as electro-deposition techniques and liquid phase reduction, electro-deposition techniques can be realized the deposition of the nano structure membrane of different-shape, but electrodeposition process relies on metallic atom is deposited in conductive substrates, film cannot independently exist, and conventional electro-deposition techniques cannot be realized the control (as the conventional aqueous solution is electroplated) of nanometer film structure simultaneously, and sedimentary condition is had relatively high expectations, the a large amount of electric energy of deposition process consumption in addition, environmental protection and energy saving is poor; Conventional liquid-phase reduction technology (such as polyalcohol method, protective agent method etc.) is to prepare the method that metal nanoparticle is conventional, but in solution, does not have the soft template of two membrane structure controls, and membrane structure just cannot realize.In prior art, there is no the associated description of utilizing ionic liquid water termination to prepare nanometer film and method that can large-scale application.
Summary of the invention
The problem existing for solving above-mentioned prior art, the present invention proposes a kind of controlled method of preparing cobalt nanometer film of ionic liquid water termination of utilizing.The special mantle formwork structure forming in conjunction with feature and the insoluble ionic liquid water termination of liquid phase reduction, can realize the controlled preparation of low temperature, and by the change to substituent adjusting and anionic group on imidazole ring, can realize the meticulous adjusting of membrane structure, meet the different needs.
For achieving the above object, technical scheme of the present invention is:
Utilize the controlled method of preparing cobalt/cobalt oxide nanometer film of ionic liquid water termination, its concrete steps are as follows:
Step 1, the KBH that the water-insoluble ionic liquid that utilizes imidazole radicals cation, compound Weakly coordinating anions to form and 0.15mol/L are newly configured
4the aqueous solution mixes in there-necked flask and ultrasonic dispersion forms the micro emulsion structure of ultra-fine dispersion; Wherein, concrete proportioning is: quality (g) and the KBH of ionic liquid
4the volume (ml) of the aqueous solution is than being 1～4/4, rear logical argon gas or nitrogen is saturated, reflux and the condition of fluid-tight under, magnetic agitation heating keep 60 ℃ of constant temperature as A liquid;
KBH in step 2, preparation and step 1
4the identical 30mmol/L cobalt acetate aqueous solution of liquor capacity is as B liquid;
Step 3, by constant pressure funnel, B liquid is dropwise added in A liquid with the speed of 2 per second, then under the condition of magnetic agitation 60～100 ℃ of isothermal reactions 1 hour until the colloidal solution of black form;
Step 4, by step 3 gained solution be cooled to room temperature and leave standstill 5 little layereds: dark oil colloidal suspension, in centre, is clear liquid up and down; Whole reaction and temperature-fall period carry out stoping the oxidation of metal Co nanometer film under argon gas or nitrogen protection;
Step 5, by ethanol washing 3-4 time centrifugal for the oily colloid of step 4 gained black, vacuum, drying at room temperature 12 hours both must Co metal nano films.
Further, Co metal nano membrane sample is placed in to tube furnace at 200 ℃, O
2/ N
2heat treatment 0.5-2h in mist, obtains cobalt oxide nanometer film structure.
Further, in described step 1, described ionic liquid is 1,3-dioctyl imidazole salts hexafluorophosphoric acid [OOIM] PF
6or 1 methyl-3 octyl group imidazole salts hexafluorophosphoric acid [C
8min] PF
6.
With respect to prior art, beneficial effect of the present invention is:
1, experimental technique is simple: under normal temperature condition, in ionic liquid water termination, pass through KBH
4reducing agent reduction realizes the preparation of cobalt/cobalt oxide nanometer film, without adding other organic stabilizer, reaction condition gentleness;
2, cobalt/cobalt oxide nanometer film structure is controllable: regulate by the structure to ionic liquid, as substituent difference, composite anion etc. on imidazole ring, the preparation of cobalt/cobalt oxide nanometer film of different structure can be realized, the instructions for use under different condition can be met; The structures shape character of material, character determines its purposes.The character such as optical, electrical, the magnetic of nano Co film, catalysis and the structure of itself are closely related.The cobalt thin film of this invention is shown excellent Co redox and Catalytic Hydrogenation Properties, and in the thickness of its performance and film and film, the particle diameter of Co particle is closely related, can realize performance optimization and adjusting by the selection of ionic liquid; The cobalt oxide membrane material of preparing by heat treatment shows high lithium storage content.
3, experiment agents useful for same environmental protection: this experiment adopts water and ionic liquid as solvent, realizes " green " completely and synthesizes, and avoids the use of complicated organic stabilizer in metal nano material building-up process, and the discharge of waste liquid is without doing complex process;
4, realize synthesizing of the metal of " clean " and oxidate nano membrane material: the adsorption capacity of ionic liquid and metal nano surface atom a little less than, the ionic liquid of metal nano material adsorption can be removed by conventional mode of washing, realize " cleaning " and synthesize, the performance of nano material is not subject to the interference of ionic liquid.
5, this method can not only realize the controlled preparation of cobalt/cobalt oxide nanometer film structure, as all applicable in Ni/NiO to Ferrious material.Same cobalt/the cobalt oxide of the implementation process nanometer film of Ni/NiO nanometer is identical.
Accompanying drawing explanation
Fig. 1 is the TEM figure of Co nanometer film under synthetic in [C8min] PF6 ionic liquid water termination, 50nm scale.
Fig. 2 is transmission electron microscope (TEM) figure of Co nanometer film under synthetic in [OOIM] PF6 ionic liquid water termination, 500nm scale.
The specific embodiment
Below in conjunction with concrete drawings and the specific embodiments, the present invention program is described in further details:
Embodiment 1: a kind of controlled method of preparing cobalt/cobalt oxide nanometer film of ionic liquid water termination of utilizing, concrete steps are: 6.00g ionic liquid (1 methyl-3 octyl group imidazole salts hexafluorophosphoric acid [C
8min] PF
6, consumption is adjustable) and KBH
4the aqueous solution of (0.15mol/L, 20mL) mixes in there-necked flask and ultrasonic dispersion forms the micro emulsion structure of ultra-fine dispersion; Rear logical Ar gas is saturated, reflux and the condition of fluid-tight under, magnetic agitation stir heating at 60 ℃ as A liquid; Cobalt acetate is configured to (30mmol/L, 20mL) aqueous solution as B liquid; By constant pressure funnel, B liquid is dropwise added in A liquid with the speed of 2 per second.Then under the condition of magnetic agitation 60 ℃ of constant temperature reaction 1 hour until the colloidal solution of black form.Reaction bulb is cooled to room temperature and leaves standstill 5 little layereds, in the middle of dark oil is suspended in, be up and down clear liquid.Whole reaction and temperature-fall period carry out stoping the oxidation of metal Co nanometer film under Ar atmosphere.The oily colloid of black is washed with alcohol 3-4 time and centrifugal, and vacuum drying at room temperature obtains Co metal nano film for 12 hours, is illustrated in figure 1 at [C
8min] PF
6the TEM figure of Co nanometer film under synthetic in ionic liquid water termination, 50nm scale.
Embodiment 2: the ionic liquid in embodiment 1 is replaced by 1,3-dioctyl imidazole salts hexafluorophosphoric acid [OOIM] PF
6, other are with embodiment 1, and result is as Fig. 2.Figure 2 shows that the PF at [OOIM]
6transmission electron microscope (TEM) figure of Co nanometer film under synthetic in ionic liquid water termination, 500nm scale; TEM figure is presented at Co nanometer film synthetic in different ionic liquid water terminations and can implementation structure regulates, and cobalt/cobalt oxide forms clean nanometer film, its thickness 1-2nm and curling in the marginal portion of film be tubular structure.By changing substituent difference on imidazole ring, change interface cope match-plate pattern characteristic and ionic liquid in the absorption of metal surface, realize the controlled preparation of Co metal nano film.Solid to pure ionic liquid, supernatant, liquid cobalt/cobalt oxide colloid and centrifugal drying carries out infrared spectrum measurement, shows all not absorption on cobalt/cobalt oxide surface of centrifugal front and back ionic liquid, realizes the preparation of cobalt/cobalt oxide nanometer film of " cleaning " completely.
The experimental technique and the implementation process that adopt by embodiment 1 and 2, and the test of properties of product structure is shown: 1., in implementation process, reaction is carried out at the temperature lower than 100 ℃, need not add other additive, reaction temperature and; 2. the structured testing to product, the substituting group difference on imidazole ring, can realize the preparation of different structure Co film, and the demonstration of infrared test result, and ionic liquid is in the nothing absorption of Co film surface.
Embodiment 3: the reaction temperature in embodiment 1 and embodiment 2 is regulated within the scope of 60-100 ℃, and other are with scheme one.Temperature has larger impact to the control of nanostructured, and reaction temperature is too low, reacts not thorough; Excess Temperature, reaction speed is too fast, and metal nucleation rate is too fast, and Co membrane structure can not be stablized formation.Reaction temperature is controlled at 60-100 ℃, by changing the adjustable Co membrane structure of reaction temperature, reacts one hour under 70 ℃ of constant temperature as reaction temperature, adds KBH
4after, Co nucleation rate is accelerated, and film formation time shortens, but the area of film and integrality all can reduce, and reaction temperature still can form nanometer film at 100 ℃;
Embodiment 4: by the Co nanometer film of gained in embodiment 1 and 2 in tube furnace in 200 ℃, O
2/ N
2heat treatment 0.5-2h in mist, obtains cobalt oxide nanometer film structure.With respect to prior art, beneficial effect of the present invention is:
1, experimental technique is simple: under normal temperature condition, in ionic liquid water termination, pass through KBH
4reducing agent reduction realizes the preparation of cobalt/cobalt oxide nanometer film, without adding other organic stabilizer, reaction condition gentleness;
2, cobalt/cobalt oxide nanometer film structure is controllable: regulate by the structure to ionic liquid, as substituent difference, composite anion etc. on imidazole ring, the preparation of cobalt/cobalt oxide nanometer film of different structure can be realized, the instructions for use under different condition can be met; The structures shape character of material, character determines its purposes.The character such as optical, electrical, the magnetic of nano Co film, catalysis and the structure of itself are closely related.The cobalt thin film of this invention is shown excellent Co redox and Catalytic Hydrogenation Properties, and in the thickness of its performance and film and film, the particle diameter of Co particle is closely related, can realize performance optimization and adjusting by the selection of ionic liquid; The cobalt oxide membrane material of preparing by heat treatment shows high lithium storage content.
3, experiment agents useful for same environmental protection: this experiment adopts water and ionic liquid as solvent, realizes " green " completely and synthesizes, and avoids the use of complicated organic stabilizer in metal nano material building-up process, and the discharge of waste liquid is without doing complex process;
4, realize synthesizing of the metal of " clean " and oxidate nano membrane material: the adsorption capacity of ionic liquid and metal nano surface atom a little less than, the ionic liquid of metal nano material adsorption can be removed by conventional mode of washing, realize " cleaning " and synthesize, the performance of nano material is not subject to the interference of ionic liquid.
5, this method can not only realize the controlled preparation of cobalt/cobalt oxide nanometer film structure, as all applicable in Ni/NiO to Ferrious material.Same cobalt/the cobalt oxide of the implementation process nanometer film of Ni/NiO nanometer is identical.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, and any variation of expecting without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (3)
1. utilize the controlled method of preparing cobalt/cobalt oxide nanometer film of ionic liquid water termination, it is characterized in that: concrete steps are as follows:
Step 1, by the water-insoluble ionic liquid that utilizes imidazole radicals cation, compound Weakly coordinating anions to form and the KBH of the fresh configuration of 0.15mol/L
4the aqueous solution mixes in there-necked flask and ultrasonic dispersion forms the micro emulsion structure of ultra-fine dispersion; Wherein, concrete proportioning is: quality (g) and the KBH of ionic liquid
4the volume (ml) of the aqueous solution is than being 1～4/4, rear logical argon gas or nitrogen is saturated, reflux and the condition of fluid-tight under, magnetic agitation heating keep 60 ℃ of constant temperature as A liquid;
KBH in step 2, preparation and step 1
4the identical 30mmol/L cobalt acetate aqueous solution of liquor capacity is as B liquid;
Step 3, by constant pressure funnel, B liquid is dropwise added in A liquid with the speed of 2 per second, then under the condition of magnetic agitation 60～100 ℃ of isothermal reactions 1 hour until the colloidal solution of black form;
Step 4, by step 3 gained solution be cooled to room temperature and leave standstill 5 little layereds: dark oil colloidal suspension, in centre, is clear liquid up and down; Whole reaction and temperature-fall period carry out stoping the oxidation of metal Co nanometer film under argon gas or nitrogen protection;
Step 5, by ethanol washing 3-4 time centrifugal for the oily colloid of step 4 gained black, vacuum, drying at room temperature 12 hours both must Co metal nano films.
2. the method for claim 1, is characterized in that, Co metal nano membrane sample is placed in to tube furnace at 200 ℃, O
2/ N
2heat treatment 0.5-2h in mist, obtains cobalt oxide nanometer film structure.
3. method as claimed in claim 1 or 2, is characterized in that, in described step 1, described ionic liquid is 1,3-dioctyl imidazole salts hexafluorophosphoric acid [OOIM] PF
6or 1 methyl-3 octyl group imidazole salts hexafluorophosphoric acid [C
8min] PF
6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105862091A (en) * | 2016-04-26 | 2016-08-17 | 陕西师范大学 | Method for preparing nanometer Ni-Fe alloy through tetrabasic ionic liquid micro-emulsion |
| CN108579748A (en) * | 2018-05-17 | 2018-09-28 | 山东大学 | A kind of catalyst cobalt protoxide and its preparation method and application |
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| CN101348936A (en) * | 2008-09-17 | 2009-01-21 | 吉林大学 | Orientational alignment carbon nano-tube and carbon coating cobalt nano-particle complex and preparation thereof |
| CN101622090A (en) * | 2007-02-27 | 2010-01-06 | 三菱麻铁里亚尔株式会社 | The synthetic method of dispersion solution of metal nanoparticle and preparation method thereof and metal nanoparticle |
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| JPH10140211A (en) * | 1996-11-14 | 1998-05-26 | Nok Corp | Production of magnetic material |
| CN1212191A (en) * | 1997-09-23 | 1999-03-31 | 上海华明高技术（集团）有限公司 | Method for manufacturing WC/CO composite nanometre powder |
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| CN105862091A (en) * | 2016-04-26 | 2016-08-17 | 陕西师范大学 | Method for preparing nanometer Ni-Fe alloy through tetrabasic ionic liquid micro-emulsion |
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| CN108579748A (en) * | 2018-05-17 | 2018-09-28 | 山东大学 | A kind of catalyst cobalt protoxide and its preparation method and application |
| CN108579748B (en) * | 2018-05-17 | 2019-12-06 | 山东大学 | Cobalt oxide for catalyst and preparation method and application thereof |
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