CN110272035A - A kind of nano cages and the application of the method and its preparation preparing nano cages with metal ion catalysis organic ligand - Google Patents
A kind of nano cages and the application of the method and its preparation preparing nano cages with metal ion catalysis organic ligand Download PDFInfo
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Abstract
The present invention relates to nano cages and the applications of a kind of method and its preparation that nano cages are prepared with metal ion catalysis organic ligand.The present invention is reaction response 2~for 24 hours under normal temperature conditions after mixing organic ligand aqueous solution and aqueous metal salt in proportion, obtain the metal organic frame presoma of granatohedron structure, then the presoma is heated to 350~500 DEG C of 1~2h of calcining at constant temperature in atmosphere of inert gases, it then proceedes to be warming up to 800~900 DEG C of 1~4h of calcining at constant temperature, through pickling, washing, drying process after cooling, nano cages are obtained.The size for the nano cages that the present invention obtains is that current report diameter is the smallest, size is about 10nm or so, in addition, ultra-fine nano cages structure prepared by the present invention has pore structure abundant, big specific surface area and excellent chemical property, and it prepares cheap, it can efficiently put into production use, possess the biggish market competitiveness.
Description
Technical field
The invention belongs to the preparation of nano material and applied technical fields, and in particular to a kind of organic with metal ion catalysis
Ligand prepares the method for nano cages and its nano cages of preparation and application.
Background technique
Currently, carbon material is widely used in the fields such as energy and environment, and such as: battery material, super electric material, undulation degree
Material, catalysis material etc., our life will be closely related with carbon material in future, and development prospect is inestimable.Reported carbon material
It is broadly divided into: one-dimensional tubulose (carbon nanotube), two-dimensional sheet (graphene), three-dimensional poroid (nano cages).From 1985
Since the synthesizing graphite alkenes such as the synthesizing carbon nanotubes such as Kroto H.W and Andre Giem in 2004, the application of carbon material is obtained
Unprecedented development, various countries researcher conduct in-depth research exploration, but related carbon to carbon nanotube and grapheme material one after another
The research of nanocages material is but rarely reported.Nano cages material is by several layers of hollow cage-shape structures formed to tens of layers of carbon-coating
It constitutes, size is generally less than 100nm, has pore structure, high-specific surface area, acid-alkali-corrosive-resisting and excellent conduction abundant and lead
Hot property can be widely used in the fields such as energy and environment material, have huge application prospect.It is produced according to China's carbon in 2017
Retribution for sins road, carbon material consumption in automobile industry (2412.7 tons), aerospace (5461.3 tons), recreation industry (3403.9 tons)
It is huge, and higher growth trend is still maintained in the use of every field.Therefore nano cages material is as novel carbon materials
Material has very high researching value.
Currently, the technology of preparing of nano cages is also very immature, the problem of many technical aspects is urgently to be resolved.Due to carbon
When nanocages only both topographically need to form specific arc, specific micro-nano hollow cage-shape structure can be just constructed, so that
Material needs harsh reaction condition and accurate consersion unit during the preparation process.Nano cages material is prepared according to existing report
Technology mainly include chemical vapor deposition, arc discharge method, hard template method, Plasma Polymerization, laser evaporation graphite
Method etc..Rough formation mechenism can be divided into two kinds: high one is being catalyzed by different metal nanoparticles to organic matter
Metallic catalysis carbon material forms cavity under the conditions of temperature, as further growth forms nano cages；Another kind needs to pass through
By specific spherical template, carbon-coating is formed in template surface first, nano cages then are can be obtained into template removal again.
Nanjing University Hu Zheng professor team has carried out preliminary exploration to nano cages material early stage, is existed by in-situ method
MgO is to obtain the nano cages that diameter is about 20nm or so by different high-temperature process by carbon source of benzene on the basis of template, is had
The experimentation of body are as follows: basic magnesium carbonate or magnesium carbonate are put into tube furnace first, under the protection of lasting inert gas, instead
It answers temperature to be gradually warmed up to 700~900 DEG C, the continual solution being passed through containing benzene is during which needed to introduce carbon source steam, carbon source
Gas brings tube furnace reaction zone into through inert gas flow, and generated in-situ bitter earth nano particle surface wraps up carbon-coating, later period
Carbon cage material (Xie K, Qin XT, Wang XZ, Hu Z.Carbon needed for pickling processes obtain is carried out to obtained powder
Nanocages as Supercapacitor Electrode Materials.Adv Mater 2012,24(7),347-
352.)；Use metal-carbonyl class compound and low-carbon class organic liquid equal in addition, patent CN 200410024700.0 was reported
Even mixing obtains being enclosed with gold in collector through electronic peristaltic pump using heating main reactor by spraying at the top of main reactor
The solid nano cages for belonging to ion, are then dissolved in acid solution, black product are dried, obtain hollow nano cages material
Material.In addition to this, patent CN 1810635A provides a kind of side for using metal ion as catalyst preparation nano cages
Method: being passed through carbonyl iron liquid for inert gas and acetylene gas mixture, will carry metal ion catalyst gas and imports main reaction
It at the top of device, is reacted by high-temperature region, iron-containing catalyst uniform particle point is continuously available in main reactor bottom collector
The combination product of cloth, is then heat-treated presoma, finally carries out acid processing and removes remainder catalyst, also can get carbon and receive
Rice cage material.Compared to these complicated synthetic technologys, Nanyang Technological University's building bear culture and education, which is awarded, has machine frame by metal
Frame is template, carries out tentatively compound with metal ion using specific organic matter first at normal temperature and obtains having for morphological rules
Machine object presoma, then carry out simple carbonization treatment and can prepare a large amount of nano cages shape material, the synthetic method is simple
Efficiently, apply all shown in battery material and super electric material excellent chemical property (Zhang H, Nai J, Yu L,
Lou X W,Metal-Organic-Framework-Based Materials as Platforms for Renewable
Energy and Environmental Applications.Joule 2017,1(1),77-107).However in these processes
The size of nano cages obtained is usually micron level, and apart from ideal nano-scale, there are also biggish gaps.
In conclusion according to the reported method for preparing nano cages of the prior art it is not difficult to find that the system of nano cages
Standby to generally use high equipment, preparation condition is harsh, low efficiency, it is difficult to which large-scale production prepares nano cages material.Secondly,
Raw material used by most methods contains higher toxicity, such as severe toxicity organic matter (hydrazine class compound, ether compound) and contain
The compound etc. of heavy metal, and there may be harmful substances, such as chloride, fluoride during the preparation process.Finally, from reality
Application aspect considers that the nano cages material being just prepared at present is diversified in specifications in appearance and size, and the size of most materials is still
In the micron-scale not, the chemical activity of carbon material is largely limited, while material specific surface area is also by large effect,
Therefore simple and effective, economical and practical, environmentally protective, the high performance nano cages material that can be mass-produced a method is found
Have great importance.
Summary of the invention
For the above-mentioned problem of the prior art and defect, the purpose of the present invention is to provide one kind to be urged with metal ion
Change organic ligand and prepares the method for nano cages and its nano cages of preparation and application.
In order to realize above-mentioned one of purpose of the invention, The technical solution adopted by the invention is as follows:
A method of nano cages being prepared with metal ion catalysis organic ligand, the method specifically includes following step
It is rapid:
(1) organic ligand is dissolved in distilled water according to the ratio, is mixing uniformly to form solution A, in which: the organic ligand
For imidazoles, methylimidazole, 2-methylimidazole, benzimidazole, phthalic acid, M-phthalic acid, benzimidazole formic acid, pyridine and
Bipyridyl is any one or more of；
(2) metal salt is dissolved in distilled water according to the ratio, is mixing uniformly to form B solution, the metal salt is zirconates, copper
In salt, molysite, zinc salt, nickel salt, cobalt salt and molybdenum salt it is any two or more；
(3) slowly B solution is added in solution A, under normal temperature conditions react 2~for 24 hours, after reaction, by product
Centrifugation, washing, obtain the metal organic frame presoma of granatohedron structure；
(4) the metal organic frame presoma is placed in high temperature furnace, and is heated under the conditions of atmosphere of inert gases
350~500 DEG C of 1~2h of calcining at constant temperature, then proceed to be warming up to 800~900 DEG C of 1~4h of calcining at constant temperature, cooled to room temperature,
It is again that products therefrom is successively dry after pickling, washing process, obtain nano cages shape powder.
Further, the proportion of above-mentioned technical proposal, step (1) organic ligand and distilled water is (3~6) quality
Part: (40~100) parts by volume；Wherein: being using g:mL as benchmark between the mass parts and parts by volume.
Preferably, above-mentioned technical proposal, the organic ligand are preferably 2-methylimidazole.
Further, the proportion of above-mentioned technical proposal, step (2) metal salt and distilled water is (1~3) mass parts:
(40~100) parts by volume；Wherein: being using g:mL as benchmark between the mass parts and parts by volume.
Further, above-mentioned technical proposal, step (2) metal salt be sulfate, nitrate, acetate, halide,
Any one or more of mixing such as phosphate, carbonate, oxalates.
Preferably, above-mentioned technical proposal, step (2) described metal salt are preferably made of cobalt salt and nickel salt, the cobalt salt with
The molar ratio of nickel salt is 1:1~6:1.
Specifically, above-mentioned technical proposal, the room temperature refer to natural room temperature condition in the four seasons, without additional cooling or
Heat treatment, general room temperature control is at 10~30 DEG C, and preferably 15~25 DEG C.
Further, above-mentioned technical proposal, for step (4) when carrying out calcination processing, the heating ramp rate is 1~10
DEG C/min, preferably 5 DEG C/min.
Further, above-mentioned technical proposal, step (4) the pickling processes time be 4~for 24 hours.
Further, above-mentioned technical proposal, step (4) the pickling solvent are the dilute hydrochloric acid or dilute sulfuric acid of low concentration, institute
The concentration for stating pickling solvent is 0.1~1.0M, is more preferably 0.5M.
Second object of the present invention is to provide the nano cages material that method described above is prepared.
Third object of the present invention is to provide nano cages material made from method described above as electrode catalyst
Application of the agent in zinc-air battery.
A kind of air electrode, including air electrode catalyst, electrolyte for air electrodes and conductive material,
In: the air electrode catalyst is nano cages material made from present invention method described above.
A kind of zinc-air battery, the battery include air electrode described above.
Compared with prior art, a kind of side preparing nano cages with metal ion catalysis organic ligand of the present invention
The nano cages and application of method and its preparation have the following beneficial effects:
(1) present invention can directly prepare carbon nanometer without expensive production equipment, common chemical synthesis and heat treatment
Cage；
(2) size for the nano cages that the present invention obtains is that current report diameter is the smallest, and size is about 10nm or so；
(3) synthesis technology of the present invention is simple, and process flow can be divided into two steps: room temperature hydro-thermal, high temperature pyrolysis；
(4) present invention, without reference to highly toxic chemical reagent and product, realizes green in the overall process of preparation
The production requirement of environmental protection.
(5) present invention prepared by ultra-fine nano cages structure have pore structure abundant, big specific surface area with it is excellent
Different chemical property, and prepare cheap, it can efficiently put into production use, possess the biggish market competitiveness.
Detailed description of the invention
Fig. 1 is the preparation process for preparing nano cages material in the embodiment of the present invention 1 with metal ion catalysis organic ligand
Flow chart.
(a), (b) are respectively the metal organic frame presoma and high temperature being prepared in the embodiment of the present invention 1 in Fig. 2
The SEM photograph of the carbon nanometer ridge powder sample obtained after processing.
Fig. 3 is the TEM photo of the carbon nanometer ridge powder sample obtained after 1 high temperature of the embodiment of the present invention is handled.
Fig. 4 is the XRD test result for the nano cages material that the embodiment of the present invention 1~3 is obtained through different high-temperature heat treatments
Figure.
(a) in Fig. 5, (b) be respectively the nano cages material that embodiment 1 and comparative example 1 obtain specific surface area (BET) and
Granularmetric analysis test result figure.
Fig. 6 is the pictorial diagram that zinc-air battery lights small bulbs in Application Example 1 of the present invention.
Fig. 7 be Application Example 1 of the present invention, compare application examples 1 in zinc-air battery cyclical stability test chart.
Specific embodiment
Below by case study on implementation, invention is further described in detail.The implementation case before being with the technology of the present invention
It puts and is implemented, provide detailed embodiment and specific operating process now to illustrate that the present invention is creative, but this
The protection scope of invention case study on implementation not limited to the following.
The present invention can get nano cages material of uniform morphology by simple preparation method, water-soluble by room temperature first
Liquid system preparation includes the organic frame presoma of metal ion, secondly generates carbon nanometer in tube furnace high temperature pyrolysis catalytic
Cage is not related to harmful substance in the entire experiment process.Since the material has unique caged pattern, hole knot abundant
Structure and higher specific surface area, may be directly applied to supercapacitor, in lithium ion battery, electrolysis water catalyst and other material.Or
Person with the compound material for obtaining unique nucleocapsid structure of other materials, is protected during the preparation process by outer layer nano cages
Internal material is protected, the stability and electron-transport efficiency of material can be effectively promoted.Such as the carrier as lithium-sulfur cell,
It can inhibit the volume expansion of sulphur while mitigating the dissolution of lithium sulphur compound, it is made to have higher capacity and cyclical stability.The material
Have many unique advantages in material structure, possesses huge application potential.
Embodiment 1
As shown in Figure 1, a kind of method for preparing nano cages with metal ion catalysis organic ligand of the present embodiment, described
Method specifically comprises the following steps: that 3.7g 2-methylimidazole is dissolved in 80mL aqueous solution first, and magnetic agitation 30min is formed
Uniform solution A, while by 1.23g cobalt nitrate (Co (NO3)2·6H2) and 0.34g nickel nitrate (Ni (NO O3)2·6H2O it) is dissolved in
In 80mL aqueous solution, magnetic agitation 30min forms Uniform B solution.Slowly B solution is poured into solution A, at room temperature
12h is reacted, purple precipitating is generated, is precipitated by supercentrifuge in 8000rpm/min, product is washed repeatedly with distilled water
It washs, dry, the metal organic frame presoma that morphological rules size is about 500nm can be obtained.Powder will be pre-processed, and (metal is organic
Frame precursor) it is contained in porcelain boat and is placed in high temperature furnace, 400 DEG C of calcining at constant temperature 2h are first heated to, then proceed to be warming up to 900
DEG C calcining at constant temperature 2h, heating rate are 5 DEG C/min, and whole process is in N2It is protected under atmosphere.Naturally it is down to room temperature, obtained product is existed
React 12h in the HCl solution of 0.5M, cleaned repeatedly with distilled water later, the dry 12h in drying box, can be obtained having a size of
10nm or so nano cages shape powder.
The carbon obtained after metal organic frame presoma and high-temperature process that the present embodiment above method is prepared is received
The SEM photograph of rice ridge powder sample is respectively as shown in Fig. 2 (a), (b).As seen from Figure 2, pass through room temperature hydro-thermal reaction, 2- first
It reacts to each other to obtain the persursor material of the granatohedron structure of morphological rules between base imidazoles and metal ion, such as schemes (a)
Shown, the surface of material is smooth, uniform in size.Using the heat treatment of different temperatures, obtain after being carbonized as shown in figure (b)
The pattern of material, material script disappears, and becomes more irregular, the particle as coarse ball is contained on the surface of material,
Even flocks together.
Contain a large amount of nano cages structure into material by the transmission electron microscope observing of high power, as shown in figure 3, size exists
10nm or so contains only several layers of carbon-coating composition, and there are certain connections between carbon cage layer.
The reaction mechanism is as follows for the present embodiment method described above:
2-methylimidazole is the important Organic Ingredients for constructing metal organic frame (ZIF-67), while playing offer carbon source
Effect.Organic ligand and metal cobalt ions will form specific granatohedron structure and obtain with the addition of nickel nitrate
Metal organic frame inside be uniformly dispersed with cobalt, nickel metal ion.By specific high-temperature heat treatment, metal ion is wherein
Catalytic action is played, amorphous carbon is promoted to change to order direction.Since cobalt, nickel bimetal ion are there are synergistic effect,
It will influence each other between different ions, with the rising of heat treatment temperature, the metal that is dispersed in organic frame body originally
The change of position will occur for ion, and gradually aggregation forms small metallic particles, and vacancy originally forms vacancy, with temperature
Rising ultimately forms cavity, obtains nano cages shape structure required for us.For existing metal nanoparticle, Ke Yiyong
Dilute hydrochloric acid carries out acidic treatment, but can not wash completely to the greatest extent, however for most of energy and materials, the presence of metal ion can be more
The effective performance for promoting material, the activity of material can be optimized by retaining some metallic particles.
Embodiment 2
A kind of method that nano cages are prepared with metal ion catalysis organic ligand of the present embodiment, step and embodiment base
This is identical, and difference is only that: the heat treatment step of the metal organic frame presoma of the present embodiment are as follows: is first heated to 400 DEG C of perseverances
Temperature calcining 2h, then proceedes to be warming up to 800 DEG C of calcining at constant temperature 2h, remaining condition is identical.
Embodiment 3
A kind of method that nano cages are prepared with metal ion catalysis organic ligand of the present embodiment, step and embodiment base
This is identical, and difference is only that: the high temperature processing step of metal organic frame presoma are as follows: 400 DEG C of calcining at constant temperature 2h are first heated to,
It then proceedes to be warming up to 1000 DEG C of calcining at constant temperature 2h, remaining condition is identical.
The nano cages material that embodiment 1-3 is obtained through different high-temperature heat treatments carries out XRD test, test result respectively
As shown in Figure 4.The chemical composition of further analysis of material finds stronger characteristic peak occur for the standard with nickel, cobalt in XRD
Position in card illustrates that, containing a certain amount of cobalt, nickel metallic element in material, the crystal property of metal is good.With temperature
Raising discovery, occur corresponding (200) crystal face of characteristic peak of carbon on 26.5 ° of position, illustrate to contain carbon in material, say
Bright carbon material is changed from amorphous state to crystal habit, the nano cages of available morphological rules under the conditions of suitable temperature
Material.
Embodiment 4
A kind of method preparing nano cages with metal ion catalysis organic ligand of the present embodiment, the method are specifically wrapped
It includes following steps: 3g methylimidazole being dissolved in 40mL aqueous solution first, magnetic agitation 30min forms uniform solution A, simultaneously will
0.5g cobalt chloride (CoCl2·6H2) and 0.5g nickel chloride (NiCl O2·6H2O it) is dissolved in 40mL aqueous solution, magnetic agitation 30min
Form Uniform B solution.Slowly B solution is poured into solution A, reacts 2h at room temperature, purple precipitating is generated, passes through height
Fast centrifuge is precipitated in 8000rpm/min, and product is washed repeatedly with distilled water, is dry, can obtain morphological rules size about
For the metal organic frame presoma of 500nm.Pretreatment powder (metal organic frame presoma) is contained in porcelain boat and is placed in
In high temperature furnace, 350 DEG C of calcining at constant temperature 2h are first heated to, then proceed to be warming up to 900 DEG C of calcining at constant temperature 1h, heating rate is 5 DEG C/
Min, whole process is in N2It is protected under atmosphere.Naturally it is down to room temperature, obtained product is reacted to 4h, later in the HCl solution of 0.5M
It is cleaned repeatedly with distilled water, dry 12h, can be obtained having a size of 10nm or so nano cages shape powder in drying box.
Embodiment 5
A kind of method preparing nano cages with metal ion catalysis organic ligand of the present embodiment, the method are specifically wrapped
It including following steps: 6g benzimidazole formic acid being dissolved in 100mL aqueous solution first, magnetic agitation 30min forms uniform solution A,
Simultaneously by 2.52g copper sulphate (CoSO4·5H2) and 0.48g zinc sulfate (Zn (SO O4)2·7H2O it) is dissolved in 100mL aqueous solution, magnetic
Power stirs 30min and forms Uniform B solution.Slowly B solution is poured into solution A, is reacted at room temperature for 24 hours, is generated purple
Color precipitating, is precipitated by supercentrifuge in 8000rpm/min, and product is washed repeatedly with distilled water, is dry, can obtain shape
The metal organic frame presoma that looks regular size is about 500nm.Pretreatment powder (metal organic frame presoma) is contained in
It is placed in high temperature furnace in porcelain boat, is first heated to 500 DEG C of calcining at constant temperature 1h, then proceed to be warming up to 800 DEG C of calcining at constant temperature 4h, risen
Warm rate is 5 DEG C/min, and whole process is in N2It is protected under atmosphere.Naturally it is down to room temperature, the dilute sulfuric acid by obtained product in 0.5M is molten
It reacts in liquid and is cleaned repeatedly with distilled water for 24 hours, later, dry 12h, can be obtained and receive having a size of 10nm or so carbon in drying box
Rice caged powder.
Comparative example 1
The preparation method of the nano cages of this comparative example, step is substantially the same manner as Example 1, and difference is only that: metal has
The high temperature processing step of machine frame presoma are as follows: be directly warming up to 900 DEG C of calcining at constant temperature 2h, remaining condition is identical.
The nano cages material that embodiment 1 and comparative example 1 obtain is subjected to specific surface area (BET) respectively and granularmetric analysis is surveyed
Examination, test result is respectively as shown in Fig. 5 (a), (b).As seen from Figure 5, the heat treatment discovery by different condition, works as heating
To 400 DEG C of heat preservation 2h, then it is warming up to 900 DEG C of obtained sample ratios of heat preservation 2h and is directly warming up to obtained by 900 DEG C of heat preservation 2h
Sample there is higher specific surface area, the lower material specific surface areas obtained of 400 DEG C of heat preservations are up to 2069m2/g.We send out simultaneously
On present pore-size distribution, the material obtained after 400 DEG C of heat preservations has microcellular structure abundant, and aperture concentrates on 10nm or less just
The diameter 10nm or so of corresponding nano cages, and for uninsulated sample, a large amount of meso-hole structure is contained in aperture, illustrates temperature
It is the important factor in order of a control pore size, can be obtained by controlling temperature program containing a large amount of nanometer basket structures
Carbon material.
Application Example 1
Nano cages material made from the embodiment of the present invention 1 is applied to the air electrode catalyst in zinc-air battery.
Zinc-air battery belongs to one kind of metal-air battery.One of electrode (referred to as air electricity of zinc-air battery
Pole) oxygen in air is absorbed during discharge, oxygen reduction reaction occurs under the effect of the catalyst, is reduced to oxygen
OH-, while metallic zinc is oxidized into Zn in another electrode (referred to as zinc electrode)2+.During the charging process, in electrolyte
OH-It can be oxidized to O under the effect of the catalyst2(oxygen evolution reaction), and Zn2+Metallic zinc is reduced in zinc electrode.Alkalinity
Reaction equation of the zinc-air battery in electric discharge are as follows:
Cathode: O2+2H2O+4e-→4OH-
Anode: 2Zn → 2Zn2++4e-
Reaction equation when charging are as follows:
Cathode: 2Zn2++4e-→2Zn
Anode: 4OH- → O2+2H2O+4e-。
The preparation process of the zinc-air battery of this application embodiment is as follows: by the catalyst of 5mg be scattered in 800 μ L ethyl alcohol and
The mixed solution of 150 μ L distilled water, is added the Nafion additive of 50 μ L, and ultrasonic 30min obtains uniform mixed solution.With shifting
Liquid rifle takes 200 μ L solution to be uniformly coated on carbon cloth (in D=1cm circle), and 60 DEG C of dryings, are assembled into zinc-air battery later,
In with 6mol/L KOH and 0.2mol/L ZnCl2As electrolyte, zine plate is assembled as cathode in blue electrical testing cabinet
Battery carries out the test of stability, and test temperature is 25 DEG C.The obtained nano cages of embodiment 1 are respectively adopted in the catalyst
Shape powder and platinum carbon；Stability test result is as shown in Figure 7.
Mainly based on noble metal, but due at high price, reserves are limited to be difficult to advise traditional air-electrode catalyst material
Modelling production, therefore we substitute precious metal material as catalysis material using nano cages material obtained, can be seen by Fig. 7
Out, nano cages material prepared by the present invention has extraordinary catalytic performance, can light small bulbs, while we are to assembling
Battery carries out the test of stability, it is found that its stability better than noble metal platinum carbon material, shows on the cyclical stability of 200h
It is excellent, there is not the decaying of performance, and then performance degradation is serious for platinum carbon material, therefore nano cages material has on practicability
There is boundless prospect.
It can be seen that can obtain carbon of uniform size using the heat treatment process of first low temperature of the invention, rear high temperature and receive
Rice caged material, specific surface area with higher and microcellular structure abundant, due to height in the process for participating in chemical reaction
Specific surface area be capable of providing a large amount of active site, while also remaining the metallic particles of part, reaction can be reduced in reaction
Chemical energy barrier is conducive to the progress for accelerating reaction.In the migration of ion and electrolyte, pore structure abundant plays important
Electrolyte and transmission of materials distance are shortened in effect, improve reaction efficiency.Special nanometer basket structure is conducive to increase the steady of material
Qualitative energy, the active material being embedded in nanocages significantly avoid external environment to internal material under the protection of carbon cage
The corrosion of material is able to extend the service life of material under severe conditions.
In conclusion the present invention prepares carbon nanometer made from the method for nano cages as metal ion catalysis organic ligand
Cage material have high specific surface area, minimum size, excellent electric conductivity and pore structure abundant, battery material,
Super electric material, fibrous material can have good application prospect in catalysis material.
Claims (10)
1. a kind of method for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that: the method is specifically wrapped
Include following steps:
(1) organic ligand is dissolved in distilled water according to the ratio, is mixing uniformly to form solution A, in which: the organic ligand is miaow
Azoles, methylimidazole, 2-methylimidazole, benzimidazole, phthalic acid, M-phthalic acid, benzimidazole formic acid, pyridine and connection pyrrole
Pyridine is any one or more of；
(2) metal salt is dissolved in distilled water according to the ratio, is mixing uniformly to form B solution, the metal salt be zirconates, mantoquita,
In molysite, zinc salt, nickel salt, cobalt salt and molybdenum salt it is any two or more；
(3) slowly B solution is added in solution A, under normal temperature conditions react 2~for 24 hours, after reaction, by product centrifugation,
Washing obtains the metal organic frame presoma of granatohedron structure；
(4) the metal organic frame presoma is placed in high temperature furnace, and it is heated under the conditions of atmosphere of inert gases 350~
500 DEG C of 1~2h of calcining at constant temperature are then proceeded to be warming up to 800~900 DEG C of 1~4h of calcining at constant temperature, cooled to room temperature, then are incited somebody to action
Products therefrom is successively dry after pickling, washing process, obtains nano cages shape powder.
2. the method according to claim 1 for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that:
The proportion of step (1) organic ligand and distilled water is (3~6) mass parts: (40~100) parts by volume；Wherein: the quality
It is using g:mL as benchmark between part and parts by volume.
3. the method according to claim 1 for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that:
The proportion of step (2) metal salt and distilled water is (1~3) mass parts: (40~100) parts by volume；Wherein: the mass parts
It is using g:mL as benchmark between parts by volume.
4. the method according to claim 1 for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that:
Step (2) metal salt is any in sulfate, nitrate, acetate, halide, phosphate, carbonate, oxalates etc.
Kind or a variety of mixing.
5. the method according to claim 1 for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that:
Step (2) described metal salt is preferably made of cobalt salt and nickel salt, and the molar ratio of the cobalt salt and nickel salt is 1:1~6:1.
6. the method according to claim 1 for preparing nano cages with metal ion catalysis organic ligand, it is characterised in that:
Step (4) the pickling processes time be 4~for 24 hours.
7. the described in any item methods for preparing nano cages with metal ion catalysis organic ligand of claim 1~6 are prepared into
The nano cages material arrived.
8. the nano cages material that any one of claim 1~6 the method is prepared is as electrode catalyst in zinc air
Application in battery.
9. a kind of air electrode, it is characterised in that: including air electrode catalyst, electrolyte for air electrodes and lead
Electric material, in which: the air electrode catalyst is the nano cages that any one of claim 1~6 the method is prepared
Material.
10. a kind of zinc-air battery, it is characterised in that the battery includes air electrode as claimed in claim 9.
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