CN105819479A - Preparation method of C12A7:e<-> electronic compound nano powder - Google Patents
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Abstract
The invention discloses a preparation method of C12A7:e<-> electronic compound nano powder. According to the preparation method, C12A7:e<-> electronic compound nano powder is directly produced through a solution method; while a conventional preparation method usually comprises two steps: obtaining insulation C12A7:O<2-> powder at first, and then reducing C12A7:O<2-> powder into C12A7:e<-> powder; the provided preparation method does not need to obtain insulation powder at first, the technology is simple, the operability is strong; moreover, the reactions are performed in a liquid phase system, C12A7:e<-> electronic compound nano powder with uniformed electrical properties is obtained, the particle size of prepared C12A7:e<-> electronic compound nano powder is in a range of 5 to 80 nm, the electric conductivity can reach 1 S/cm; the provided preparation method does not use dangerous materials adopted by the conventional methods, the dangerous materials are active, explosive, and flammable, thus the preparation method is very safe; in the provided preparation method, pure phase C12A7:e<-> electronic compound can be obtained at a lowest temperature of 700 DEG C, the energy consumption is reduced during the preparation process, the preparation cost is low, and the preparation method is suitable for industrial large-scale application therefore.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, relate to the preparation method of calcium aluminum electron compound, be specifically related to a kind of C12A7:e-
The preparation method of electron compound nanometer powder.
Background technology
Element abundant species on the earth, but in view of factors such as radiation, toxicity and reserves, real actual spendable only 60-70
Kind, wherein earth's crust reserves relative abundance has more than 20 to plant.The development of the following mankind, is faced with the energy, resource management and environment etc.
Series of problems, occurs by laying in material that is abundant elementary composition and that have innovation meaning in the earth's crust in the urgent need to some.
Electron compound refer to a class using electronics as the ionic compound material of anion, it is in basic research and actual application
There is important value.The most conventional organic and inorganic electronic compound all also exists asking of poor stability in air or dampness
Topic.Therefore, develop good stability, excellent performance novel electron compound significant.
Electron compound [Ca24Al28O64]4+(e-)4, it is abbreviated as C12A7:e-, belong to CaO-Al2O3Mixed oxide series, group
Becoming element O, Al and Ca, corresponding reserves lay respectively in the earth's crust the first, the 3rd and the 5th.Each list in C12A7 material
Unit is connected with each other the positively charged framework formed, 4 in 12 cage constructions by the cage construction of 12 nanoscales
There is electronics in cage construction, just define C12A7:e-Electron compound.C12A7:e-The crystal structure that electron compound is unique
Give the performance of its excellence.C12A7:e-Electron compound at room temperature has metallic conduction characteristic.C12A7:e-Electron compound
Another feature is that work function is low, and about 2.4eV is similar with metallic potassium, but C12A7:e-The chemical property of electron compound with
Metal is compared more stable.Meanwhile, C12A7:e-Electron compound the following is chemically stable at 400 DEG C.C12A7:e-Electronization
Compound powder is executed because the unique stability of material and low work function characteristic make it be expected to become good electronics in chemical catalysis reacts
Main, apply at industry ammonia, CO2Decomposition and the reaction such as synthesis in, can effectively reduce the reaction temperature in preparation process and pressure
Power, has the biggest application potential.C12A7:e-Electron compound power applications in the catalyst, on the one hand needs to obtain to the greatest extent
Possible big surface area, on the other hand needs higher electric conductivity.
2003, the thin wild elegant male professor seminar of Tokyo Institute of Technology prepared inorganic electron compound C12A7:e first-,
The stable electron compound obtained first under conditions of becoming in atmosphere and being higher than room temperature.C12A7:e-The system of electron compound
Standby condition is the harshest.The preparation C12A7:e of report at present-First the method for electron compound powder is prepares insulation
C12A7:O2-Powder, then uses reducing agent to anneal under the conditions of high temperature etc. and is prepared from.The C12A7:O of insulation2-Each list
In the cage construction framework of 12 nanoscales of unit, have in two cage constructions and be respectively present an O2-Oxonium ion.Pass through thing
Reason or the method for chemistry, by the O in structure2-Ion replaces by other anion, such as halide ion (F-, Cl-), hydroxyl
Ion (OH-), superoxide radical (O2 -)、O-、S2-And H-, may result in the injection of electronics, thus obtain C12A7:e-Electronics
Compound.Within such as 2012, thin wild elegant male professor seminar (nature chemistry, 2012,4:934-940) uses solid state reaction
Method prepares C12A7:O2-Powder, then evacuation and reducing agent Ca metal sealing are in glass tubing, finally by surface residual
Ca grinds off, the C12A7:O obtained2-The specific surface area of electron compound powder is 1m2/g.The method needs at high vacuum condition
The active metal (Ca) of lower employing, as reducing agent, has danger.Although additionally, ball milling can effectively increase in the method
Add surface area, but the cage construction on surface will certainly be destroyed, thus form insulating barrier suppression electron donating ability.This class in 2014
Topic group uses hydro-thermal reaction to prepare C12A7:O2-Powder, after at 600-1000 DEG C vacuum (1 × 10-4Pa) process, then will obtain
Powder with excess CaH2Mixing, during successively vacuum-pumping density is encapsulated in Ta pipe and glass tubing, keeping vacuum is (1 × 10-4Pa),
Process 15 hours at 600-700 DEG C, obtain C12A7:e-Electron compound powder (ACS Catalysis, 2014,4:
674-680).The C12A7:e that the method obtains-The specific surface area of electron compound powder is 20m2/ g, but CaH2Belong to dangerous
Combustible material, needs condition of high vacuum degree and the time of process long simultaneously in experiment.Patent CN 102307812 A provide a kind of containing leading
The electrically manufacture method of the oxide of mayenite, in the method, needs powder temperature more than 1210 DEG C in hydrogen-containing gas
Lower calcining, then to the ultraviolet that oxide illumination wavelength is 140-380nm containing mayenite, thus obtains the calcium aluminum of electric conductivity
Stone-type compound.
In sum, overcome employing fine vacuum, explosion hazard gases, the deficiency of active flammability hazard material in existing preparation process,
Explore synthesis C12A7:e-The straightforward procedure of electron compound powder, it is achieved industrial inexpensively and in a large number produce, remains C12A7:e-
A major challenge in research.
Summary of the invention
The technical problem to be solved is: for the deficiencies in the prior art, it is provided that a kind of technique is simple, workable,
Safe and reliable C12A7:e-The preparation method of electron compound nanometer powder.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of C12A7:e-The system of electron compound nanometer powder
Preparation Method, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al=x:y, weigh the addition of C a source and Al source and be configured to mixture, wherein, 11≤x≤12,
13≤y≤14, described Ca source is CaO, CaCO3、Ca(OH)2、Ca(NO3)2With Ca (COOCH)2In one or two
Kind, described Al source is Al2O3、Al(OH)3、Al(NO3)3With Al (COOCH)3In one or both；
(2) mixture preparation obtained and organic solvent are according to 1:(50-120) mixed in molar ratio, stir at 20-60 DEG C
Mix and mix homogeneously, obtain mixed solution；
(3) mixed solution is heated at 100-300 DEG C drying in 1-6 hour, obtain initial powder；
(4) under non-oxidizing atmosphere, by initial powder in the ramp of 3-8 DEG C/min, first it is incubated at 450-600 DEG C
1-3 hour, then it is warming up to 700-1550 DEG C of calcining 0.5-10 hour, obtain the C12A7:e of black-Electron compound nanometer powder.
Further, possibly together with doped source in the mixture that step (1) is prepared, described mixture is by Ca source, Al source and mixes
Miscellaneous source according to Ca:Al:M=x:y:z atom measure ratio weigh and mix, wherein, M represents doped chemical, M be Si,
At least one in Ge, Sn, Pb, Ga, In, Cu, Ag, Au, F, Cl and Br, described doped source be containing Si,
The compound of at least one element in Ge, Sn, Pb, Ga, In, Cu, Ag, Au, F, Cl and Br, 11≤x≤12,
13≤y≤14,0.01≤z≤1, and x, y and z meet x+y+z=26.
Further, possibly together with chelating agen in the mixed solution that step (2) obtains, this mixed solution is prepared by step (1)
The mixture arrived and organic solvent and chelating agen are according to 1:(50-120): after the mixed in molar ratio of (1-30), stir at 20-60 DEG C
Mix and mix homogeneously obtains.
As preferably, described organic solvent is the one in ethanol, isopropanol, ethylene glycol, ethanolamine and diethanolamine.Enter
One step ground, described ethanol be volume fraction be the ethanol of 95%, described isopropanol, ethylene glycol and ethanolamine are analytical pure,
Described diethanolamine is chemical pure.
As preferably, described chelating agen is the one in citric acid, glacial acetic acid, formic acid and benzoic acid.Further, described
Citric acid, glacial acetic acid, formic acid and benzoic acid be analytical pure.
As preferably, described non-oxidizing atmosphere is the one in nitrogen, argon and argon hydrogen gaseous mixture, described argon hydrogen mixing
Argon and the volume ratio of hydrogen in gas are 92:8 or 96:4.
Compared with prior art, it is an advantage of the current invention that:
1, the C12A7:e that the present invention provides-The preparation method of electron compound nanometer powder is a kind of solwution method, and the present invention is by molten
Liquid method directly obtains C12A7:e-Electron compound nanometer powder product, first obtains insulation C12A7:O with existing2-Powder, again general
It is reduced to C12A7:e-The preparation method of the big step of routine two of powder compares, it is to avoid first obtain the step of insulating powder, work
Skill is simple, workable；
2, the course of reaction of the inventive method is carried out in liquid-phase system, and organic solvent and chelating agen contact all with Ca source and Al source
Even, it is simple to obtain the C12A7:e with uniform electrical performance-Electron compound nanometer powder, the inventive method prepares
C12A7:e-The particle diameter of electron compound nanometer powder is between 5-80nm, and electrical conductivity is up to 1S/cm；
3, the present invention can avoid existing C12A7:e-Fine vacuum that electron compound powder preparation method is used, explosion hazard gases, work
Sprinkling the use of flammability hazard material, safety is high；
4, the inventive method is minimum just can obtain pure phase C12A7:e at 700 DEG C-Electron compound, contributes to reducing in preparation process
Energy consumption, preparation cost is low, be suitable for industrialization large-scale application.
Accompanying drawing explanation
Fig. 1 is the C12A7:e that embodiment 1 prepares-The XRD figure of electron compound nanometer powder；
Fig. 2 is the C12A7:e of the amplification 40,000 times that embodiment 1 prepares-The TEM figure of electron compound nanometer powder；
Fig. 3 is the C12A7:e of the amplification 500,000 times that embodiment 1 prepares-The TEM figure of electron compound nanometer powder；
Fig. 4 is the C12A7:e that embodiment 1 prepares-The electron paramagnetic resonance spectrum figure of electron compound nanometer powder.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The preparation method of the C12A7:e-electron compound nanometer powder of embodiment 1, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al=12:14, weigh the addition of C a (NO3)2·4H2O and Al (NO3)3·9H2O prepares
Resulting mixture；
(2) mixture preparation obtained and ethylene glycol and citric acid are according to the mixed in molar ratio of 1:120:30, stir at 20 DEG C
Mix and mix homogeneously, obtain mixed solution；
(3) mixed solution is heated at 200 DEG C drying in 6 hours, obtain initial powder；
(4) in a nitrogen atmosphere, by initial powder with the ramp of 5 DEG C/min, first at 450 DEG C, it is incubated 1 hour, then
It is warming up to 700 DEG C calcine 1 hour, obtains the C12A7:e of the black of embodiment 1-Electron compound nanometer powder.
Through measuring and calculating, the C12A7:e of embodiment 1-The particle diameter of electron compound nanometer powder is 5nm, and specific surface area value is 31m2g-1,
Electrical conductivity is 0.5S/cm.
The C12A7:e of embodiment 1-The XRD figure of electron compound nanometer powder is shown in that Fig. 1, TEM figure is shown in Fig. 2 and Fig. 3, electronics
Paramagnetic resonance spectrogram is shown in Fig. 4.It can be seen from figure 1 that the C12A7:e obtained by preparation method of the present invention-Electron compound nano powder
End is the C12A7 powder of pure phase, calculates according to Scherrer formula, and the particle diameter of this powder is 5nm.Fig. 2 and Fig. 3 can be bright
Show and find out that the powder that preparation method of the present invention obtains is nanometer powder.Formant display powder in Fig. 4 there is unpaired electron to deposit
, it was demonstrated that the powder that preparation method of the present invention prepares is electron compound.
The preparation method of the C12A7:e-electron compound nanometer powder of embodiment 2, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al=12:14, weigh the addition of C aCO3With Al (OH)3It is configured to mixture；
(2) mixture preparation obtained and ethanol and glacial acetic acid are according to the mixed in molar ratio of 1:50:30, stir also at 40 DEG C
Mix homogeneously, obtains mixed solution；
(3) mixed solution is heated at 150 DEG C drying in 6 hours, obtain initial powder；
(4) under an argon atmosphere, by initial powder with the ramp of 5 DEG C/min, first at 500 DEG C, it is incubated 1 hour, then
It is warming up to 1450 DEG C calcine 1 hour, obtains the C12A7:e of the black of embodiment 2-Electron compound nanometer powder.
Through measuring and calculating, the C12A7:e of embodiment 2-The particle diameter of electron compound nanometer powder is 5nm, and electrical conductivity is 1.0S/cm.
The preparation method of the C12A7:e-electron compound nanometer powder of embodiment 3, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al=12:14, weigh the addition of C a (COOCH)2With Al (COOCH)3It is configured to mix
Compound；
(2) mixture preparation obtained and isopropanol and formic acid are according to the mixed in molar ratio of 1:120:15, stir at 60 DEG C
And mix homogeneously, obtain mixed solution；
(3) mixed solution is heated at 250 DEG C drying in 6 hours, obtain initial powder；
(4) in a nitrogen atmosphere, by initial powder with the ramp of 5 DEG C/min, first at 600 DEG C, it is incubated 1 hour, then
It is warming up to 1150 DEG C calcine 1 hour, obtains the C12A7:e of the black of embodiment 3-Electron compound nanometer powder.
Through measuring and calculating, the C12A7:e of embodiment 3-The particle diameter of electron compound nanometer powder is 60nm, and specific surface area value is 19
m2g-1, electrical conductivity is 0.5S/cm.
The preparation method of the C12A7:e-electron compound nanometer powder of embodiment 4, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al:Sn=12:13:1, weigh the addition of C a (NO3)2·4H2O、Al(NO3)3·9H2O and
SnCl4·5H2O is configured to mixture；
(2) mixture preparation obtained and ethanolamine are according to the mixed in molar ratio of 1:60, stir and mix homogeneously at 60 DEG C,
Obtain mixed solution；
(3) mixed solution is heated at 300 DEG C drying in 6 hours, obtain initial powder；
(4) in a nitrogen atmosphere, by initial powder in the ramp of 5 DEG C/min, first at 500 DEG C, it is incubated 2 hours, then
It is warming up to 1500 DEG C calcine 1 hour, obtains the C12A7:e of the black of embodiment 4-Electron compound nanometer powder.
Through measuring and calculating, the C12A7:e of embodiment 4-The particle diameter of electron compound nanometer powder is 60nm, and electrical conductivity is 0.5S/cm.
The preparation method of the C12A7:e-electron compound nanometer powder of embodiment 5, comprises the following steps:
(1) measure ratio according to the atom of Ca:Al:Cu=11:14:1, weigh the addition of C a (NO3)2·4H2O、Al(NO3)3·9H2O and
Cu(NO3)3·5H2O is configured to mixture；
(2) mixture preparation obtained and diethanolamine and benzoic acid are according to the mixed in molar ratio of 1:80:5, stir at 60 DEG C
Mix and mix homogeneously, obtain mixed solution；
(3) mixed solution is heated at 300 DEG C drying in 3 hours, obtain initial powder；
(4) under the argon hydrogen gaseous mixture atmosphere that volume ratio is 92:8 of argon and hydrogen, by initial powder in the speed of 5 DEG C/min
Heat up, first at 550 DEG C, be incubated 1 hour, then be warming up to 1550 DEG C of calcinings 0.5 hour, obtain the black of embodiment 5
C12A7:e-Electron compound nanometer powder.
Through measuring and calculating, the C12A7:e of embodiment 5-The particle diameter of electron compound nanometer powder is 80nm, and electrical conductivity is 0.03S/cm.
In the various embodiments described above, the ethanol that ethanol can use volume fraction to be 95%, citric acid, glacial acetic acid, formic acid, benzoic acid,
Isopropanol, ethylene glycol and ethanolamine can use analytical pure, and diethanolamine can use chemical pure.
Claims (8)
1. a C12A7:e-The preparation method of electron compound nanometer powder, it is characterised in that comprise the following steps:
(1) measuring ratio according to the atom of Ca:Al=x:y, weigh the addition of C a source and Al source and be configured to mixture, wherein, 11≤x≤12,13≤y≤14, described Ca source is CaO, CaCO3、Ca(OH)2、Ca(NO3)2With Ca (COOCH)2In one or both, described Al source is Al2O3、Al(OH)3、Al(NO3)3With Al (COOCH)3In one or both；
(2) mixture preparation obtained and organic solvent are according to 1:(50-120) mixed in molar ratio, at 20-60 DEG C, stirring mix homogeneously, obtain mixed solution；
(3) mixed solution is heated at 100-300 DEG C drying in 1-6 hour, obtain initial powder；
(4) under non-oxidizing atmosphere, by initial powder in the ramp of 3-8 DEG C/min, first at 450-600 DEG C, it is incubated 1-3 hour, then is warming up to 700-1550 DEG C of calcining 0.5-10 hour, obtain the C12A7:e of black-Electron compound nanometer powder.
A kind of C12A7:e the most according to claim 1-The preparation method of electron compound nanometer powder, it is characterized in that in the mixture that step (1) is prepared possibly together with doped source, described mixture is by Ca source, Al source and doped source are measured ratio according to the atom of Ca:Al:M=x:y:z and are weighed and mix, wherein, M represents doped chemical, M is Si, Ge, Sn, Pb, Ga, In, Cu, Ag, Au, F, at least one in Cl and Br, described doped source is containing Si, Ge, Sn, Pb, Ga, In, Cu, Ag, Au, F, the compound of at least one element in Cl and Br, 11≤x≤12, 13≤y≤14, 0.01≤z≤1, and x, y and z meets x+y+z=26.
A kind of C12A7:e the most according to claim 1-The preparation method of electron compound nanometer powder, it is characterized in that in the mixed solution that step (2) obtains possibly together with chelating agen, this mixed solution is prepared the mixture and organic solvent obtained and chelating agen according to 1:(50-120 by step (1)): after the mixed in molar ratio of (1-30), at 20-60 DEG C, stirring mix homogeneously obtain.
4. according to a kind of C12A7:e according to any one of claim 1-3-The preparation method of electron compound nanometer powder, it is characterised in that described organic solvent is the one in ethanol, isopropanol, ethylene glycol, ethanolamine and diethanolamine.
A kind of C12A7:e the most according to claim 4-The preparation method of electron compound nanometer powder, it is characterised in that described ethanol be volume fraction be the ethanol of 95%, described isopropanol, ethylene glycol and ethanolamine is analytical pure, and described diethanolamine is chemical pure.
6. according to a kind of C12A7:e according to any one of claim 1-3-The preparation method of electron compound nanometer powder, it is characterised in that described chelating agen is the one in citric acid, glacial acetic acid, formic acid and benzoic acid.
A kind of C12A7:e the most according to claim 6-The preparation method of electron compound nanometer powder, it is characterised in that described citric acid, glacial acetic acid, formic acid and benzoic acid are analytical pure.
8. according to a kind of C12A7:e according to any one of claim 1-3-The preparation method of electron compound nanometer powder, it is characterised in that described non-oxidizing atmosphere is the one in nitrogen, argon and argon hydrogen gaseous mixture, the described argon in argon hydrogen gaseous mixture and the volume ratio of hydrogen are 92:8 or 96:4.
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Cited By (5)
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| CN107338472A (en) * | 2017-06-28 | 2017-11-10 | 北京工业大学 | The preparation method of new oxide semiconductor polycrystal block |
| CN109306521A (en) * | 2018-09-03 | 2019-02-05 | 北京工业大学 | Conductivity type Ca12Al14O32:2e-The manufacturing method of electron compound |
| CN115141078A (en) * | 2022-06-30 | 2022-10-04 | 浙江工业大学 | Application of electronic compound as catalyst in reaction for synthesizing chloroethylene by hydrochlorinating acetylene |
| CN116177579A (en) * | 2023-03-20 | 2023-05-30 | 深圳市诺安智能股份有限公司 | Conductive compound S12A7:e - Is prepared by the preparation method of (2) |
| CN116253558A (en) * | 2023-03-20 | 2023-06-13 | 深圳市诺安智能股份有限公司 | Preparation method of graphene-coated electronic compound and preparation method of film |
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