CN105036173B - A kind of preparation method of core-shell structure particles material - Google Patents
A kind of preparation method of core-shell structure particles material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of core-shell structure particles material, selection isopotential point differs greatly first and the respectively two kinds of particles of nanoscale and micron particle size is respectively as interlayer material and nucleome material, two kinds of particles is set to form core interlayer composite particles skeleton by electrostatic self-assembled in aqueous, then in core interlayer composite particles Surface Creation shell, finally grind and sieve to obtain from the inside to the outside as the core-shell structure particles material of core interlayer shell structurre.The preparation method introduces nanometer interlayer in core shell structure, and it is not high to overcome nucleome and the shell bond strength of the core-shell structure particles material of script, or the problem of directly in conjunction with generation accessory substance, reaches the purpose of controllable preparation high-performance granular materials.
Description
Technical field
The invention belongs to applications to nanostructures and functional material synthesis field, more particularly, to a kind of core shell structure
The preparation method of granular materials.
Background technology
Core-shell structure material has many unique physics and chemical characteristic, in super-hydrophobic surface coating, materialogy, change
The fields such as, magnetics, electricity, optics, biomedicine, catalysis all have potential application value.Chemical chain technology is a kind of new
The fossil fuel CO of type2Emission-reduction technology, with potential reduction emission reduction cost, raising fuel energy utilization ratio, reduction and take off
Except advantages such as other atmosphere pollutions, its key issue is the research and development of the high-performance carrier of oxygen.
The nano composite material of core shell structure typically by center core and be coated on the shell of outside and form, but common core
In shell structure, active shell layer and inertia nucleome or active nucleome and inertia shell directly contact, it may occur that active component and inertia
The chemical reaction of carrier, active component content reduction, inert carrier stability and intensity decreases are directly resulted in, thus cause material
Performance degradation.
Nanometer interlayer is introduced in the synthesis of core-shell material, the hierarchy of core-interlayer-shell is formed, can greatly promote
The intensity and performance of material.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of core-shell structure particles material and its
Self-assembling method, formed using the isopotential point nature difference of nucleome material and interlayer material by electrostatic self-assembled high performance
Granular materials.The preparation process energy-conserving and environment-protective of the present invention, the core-shell structure particles material of preparation are used as the carrier of oxygen, CO2
Absorbent or catalyst etc., there is the advantages of big load capacity, activity height, stable performance, have extended cycle life.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of preparation of core-shell structure particles material
Method, it is characterised in that specific steps include：
Step 1：Nucleome material and interlayer material are dispersed in water, and it is that pH ' makes the core to adjust pH value with acid or alkali
Body material and the interlayer material fully assemble, to obtain the suspension of core-interlayer composite particles；
Wherein, the nucleome material be 1 μm~100 μm of particle diameter micron particles, the interlayer material be particle diameter be 1nm~
100nm nano particle, the mass ratio of the nucleome material and the interlayer material are more than or equal to 2:1；IEP1And IEP2Respectively
The isopotential point of the nucleome material and the interlayer material, and IEP1With IEP2Difference be more than or equal to 2.5；PH ' is in IEP1With
IEP2Between, and when pH value is pH ', the electrical opposite and difference of the Zeta potential of nucleome material and interlayer material is maximum；
Step 2：In core-interlayer composite particles surface deposition shell raw material, and generation shell is calcined, finally grinding screening
Obtain required core-shell structure particles material.
Preferably, acid is acetic acid, hydrochloric acid or nitric acid described in step 1, and the alkali is ammoniacal liquor.
Preferably, the mass ratio of nucleome material and interlayer material is 3:1~15:1.
Preferably, IEP1With IEP2Difference be more than or equal to 5.
Preferably, metal oxide shell is prepared using hydro-thermal method in step 2, detailed process is as follows：
Metal organic salt is added into the suspension of step 1 is completely dissolved it, is calcined after fully drying,
Finally grinding screening obtains required core-shell structure particles material；
In calcination process, metal organic salt decompose generation metal oxide as shell while, also generation vapor with
And carbon dioxide is as accessory substance.
But during metal oxide is prepared, the metal organic salt of solubility is often can not find as raw material, or
Metal organic salt is sufficiently expensive corresponding to person；Therefore, the detailed process of step 2 can also be preferably as follows：
Metal nitrate and fuel are added into the suspension of step 1 is completely dissolved it, is carried out after fully drying
Calcining, finally grinding screening obtain required core-shell structure particles material；
Wherein, the fuel is metal acetate salt or urea, and in calcination process, metal nitrate and the fuel are completely anti-
While metal oxide should be generated as shell, nitrogen, vapor and carbon dioxide are also generated as accessory substance.
Assuming that metal is X, chemical valence is+n；When fuel is metal acetate salt, reaction equation is as follows：
16X(NO3)n+10X(CH3COO)n→13A2On+8nN2+20nCO2+15nH2O
Wherein it is possible to from the acetate and nitrate of different metal, to generate mixed-metal oxides as shell.
When fuel is urea, reaction equation is as follows：
6X(NO3)n+5nCO(NH2)2→3X2On+5nCO2+10nH2O+8nN2
As it is further preferred that metal nitrate and fuel carry out dispensing according to stoichiometric proportion during complete reaction.
Shell raw material is in respectively metal organic salt, metal nitrate and metal acetate salt or metal nitrate and urea
When, its calcination reaction condition and indifference；So in actual fabrication process, Shell Materials can be arbitrarily from three groups of materials above
It is one or more groups of in material.
Present invention also offers a kind of carrier of oxygen obtained with the preparation method, it is characterised in that：
The nucleome material is the α phases Al of 37 μm~75 μm particle diameters2O3Particle, the interlayer material be particle diameter 10nm~
100nm Rutile Type TiO2The mass ratio of nano particle, the nucleome material and the interlayer material is 3.5:1；The shell
Layer raw material is fuel and metal nitrate, and fuel is urea, and metal nitrate is copper nitrate, and both mol ratios are 5:3.
Present invention also offers a kind of CO obtained with the preparation method2Absorbent, it is characterised in that：
The nucleome material is the α phases Al of 37 μm~75 μm particle diameters2O3Particle, the interlayer material be particle diameter 10nm~
100nm Rutile Type TiO2The mass ratio of nano particle, the nucleome material and the interlayer material is 3:1；The shell
Raw material is calcium acetate and calcium nitrate, and both mol ratios are 5:8.
In general, by the contemplated above technical scheme of the present invention compared with prior art, have below beneficial to effect
Fruit：
1st, using the isopotential point nature difference of particle, interlayer is self-assembly of on nucleome material, self assembling process is not
Need the complicated reaction condition such as surfactant, HTHP；It is straight with Shell Materials that the introducing of interlayer avoids nucleome material
Connect and combine to form accessory substance, improve the stability and performance of core-shell material；
2nd, during preparing interlayer, the thickness of interlayer can be controlled according to the mass ratio of nucleome material and interlayer material,
Reach the effect of controllable preparation interlayer；
3rd, combustion reaction generation shell occurs using fuel and metal nitrate, solves and be often difficult in conventional hydrothermal method
The problem of finding suitable metal organic salt；The heat that combustion reaction is released can reduce the energy resource consumption in calcination processing, simultaneously
The pollutant NOx that nitrate decomposes release is significantly reduced, there is effects of energy conservation and environmental protection.
4th, the carrier of oxygen and CO prepared with this method2Absorbent, functional, oxygen carrier amount and CO2The close ideal of uptake
Value.
Brief description of the drawings
Fig. 1 is the self assembling process schematic diagram of core-shell structure particles material of the present invention.
Fig. 2 a and Fig. 2 b are the embodiment 1 that micro-electrophoresis apparatus measures and the nucleus material of embodiment 3 and Shell Materials respectively
Zeta potential and the relation of disperse system pH value.
Fig. 3 is the carrier of oxygen combustion process tail gas that the carrier of oxygen is prepared with traditional sol-gal process in the embodiment of the present invention 1
Monitoring result contrasts.
Fig. 4 is nm-TiO in Example 1 and Example 2 of the present invention2Particles coat μm-Al2O3The transmission electron microscopy of particle
Figure.
Fig. 5 is the profile scanning sem image and distribution diagram of element of carrier of oxygen particle in the embodiment of the present invention 1.
Fig. 6 is CO in the embodiment of the present invention 22The scanning electron microscope image and distribution diagram of element of absorbent.
Fig. 7 a are oxygen carrier amount variation diagrams in 15 oxygen releases of the carrier of oxygen in the embodiment of the present invention 1-oxygen uptake circulation, and Fig. 7 b are the oxygen
X ray diffracting spectrum of the carrier under three kinds of different conditions, Fig. 7 c are the X ray diffracting spectrums of comparative example.
Fig. 8 a are CO in the embodiment of the present invention 2220 carbonatings of absorbent-calcination cycle thermogravimetric test result, Fig. 8 b are
The CO2X ray diffracting spectrum of the absorbent under two kinds of different conditions.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
Embodiment 1CuO (77.5wt%)-TiO2(5wt%)-Al2O3(17.5wt%) carrier of oxygen
Step 1：The α phases Al of 37 μm~75 μm of particle size range is screened out with the sieve of 400 mesh and 200 mesh2O3Particle is standby
(hereinafter referred to as μm-Al2O3), take sample therein to measure the Zeta electricity under different pH value aqueous conditions on micro-electrophoresis apparatus
Position and then the isopotential point IEP for determining particleA；The TiO of particle size range 10nm~100nm Rutile Type is chosen simultaneously2Nanometer
Grain sample (hereinafter referred to as nm-TiO2), determine isopotential point IEP with same methodT, as shown in Figure 2 a.
Step 2：300mL deionized waters are injected into beaker, 80 DEG C are heated in water-bath, then add μm-Al2O3
Particle 17.5g stirs, and adds nm-TiO2Particle 5.0g is uniformly mixed.Adjusted with dust technology and ammoniacal liquor scattered
The acid-base value of system, the pH value for making disperse system are 6, now μm-Al2O3Particle and nm-TiO2The Zeta potential of particle it is electrical opposite
And difference is maximum (as shown in Figure 2 a)；Due to a μm-Al2O3And nm-TiO2Particle surface has stronger positive potential and negative electricity respectively
Position, they condense under the common sucking action of Van der Waals for and electrostatic force, form μm-Al2O3By nm-TiO2Bag
The core covered-interlayer composite particles, and the cohesion between particle of the same race is suppressed by stronger electrostatic repulsion effect.
Step 3：Urea crystal 97.5g is added into disperse system makes it fully dissolve as fuel, lasting stirring, urea
Addition can by steric hindrance act on be stabilized particle clusters；Add Cu (NO3)2·3H2O crystal 235.4g makees
For the raw material of shell, lasting stirring makes it fully dissolve；Urea is just complete with copper nitrate according to fuel as fuel, its addition
Stoichiometric ratio during full burning is determined, beaker is moved into air dry oven, after drying 24h under the conditions of 80 DEG C, prepared
Obtain core-shell structure particles material precursor；The presoma is transferred in porcelain boat, porcelain boat is then put into Muffle furnace internal program
Heating is lighted and calcined；The heating rate that Muffle furnace sets 20 DEG C/min is heated to 950 DEG C from room temperature, and 2h is calcined at 950 DEG C.
Following total whole combustion process of bag thermochemical equation approximate representation can be used：
3Cu(NO3)2+5CO(NH2)2→3CuO+5CO2+10H2O+8N2；kJ/mol；
In course of reaction, urea occurs combustion reaction as fuel and copper nitrate and forms endogenous pyrogen, not only saves outside heat
The consumption of amount can also significantly shorten calcination time；Product is annealed and cooled down, is ground, screens out a diameter of 75 μm~300 μm of
Grain, that is, obtain required core-shell structure particles material, the material can be used for chemical chain reaction as the carrier of oxygen.
Tail gas monitoring discovery is carried out to the combustion process of embodiment 1, the NOx that whole process is discharged coagulates with traditional colloidal sol
Glue method preparation process is compared to have and significantly reduced, and has obvious environment friendly, as shown in Figure 3.
Embodiment 2CaO (80wt%)-TiO2(5wt%)-Al2O3(15wt%) CO2Absorbent
Step 1：It is identical with the step of embodiment 1 one.
Step 2：Identical with the step of embodiment 1 two, difference is a μm-Al2O3The quality of particle is 15.0g.
Step 3：Identical with the step of embodiment 1 three, difference is with 97.5gCa (CH3COO)2·H2O powder and
207.5gCa(NO3)2·4H2O crystal substituted ureas and Cu (NO3)2·3H2O occurs following anti-as shell raw material during being somebody's turn to do
Should：
5Ca(CH3COO)2+8Ca(NO3)2→13CaO+20CO2+15H2O+8N2；
The particle size range screened out is 30 μm~300 μm, finally obtains required core-shell structure particles material, the material can
As CO2Absorbent.
Embodiment 3CuO (80wt%)-MgO (2wt%)-Al2O3(18wt%) carrier of oxygen
Step 1：Identical with the step of embodiment 1 one, difference is (to be hereinafter referred to as with 20nm~80nm MgO particles
Nm-MgO nm-TiO) is replaced2, determine isopotential point IEPM, the acid-base value for adjusting solution is 11, as shown in Figure 2 b.
Step 2：Identical with the step of embodiment 1 two, difference is a μm-Al2O3The quality of particle is 18.0g, nm-MgO
The quality of particle is 2.0g, and the pH value for adjusting disperse system is equal to 11.
Step 3：Identical with the step of embodiment 1 three, difference is that the quality of fuel urea is 100.7g, Cu (NO3)2·
3H2The quality of O crystal is 243.0g.
Embodiment 4CaO (80wt%)-MgO (2wt%)-Al2O3(18wt%) CO2Absorbent
Step 1：It is identical with the step of embodiment 3 one.
Step 2：Identical with the step of embodiment 3 two, difference is, the acid of disperse system is adjusted with watery hydrochloric acid and ammoniacal liquor
Basicity.
Step 3：Identical with the step of embodiment 1 three, difference is that fuel is 143.0g urea, and metal nitrate is
337.4g Ca(NO3)2·4H2O crystal.
Embodiment 5CaO (80wt%)-TiO2(2wt%)-Al2O3(18wt%) CO2Absorbent
Step 1：It is identical with the step of embodiment 1 one.
Step 2：Identical with the step of embodiment 1 two, difference is a μm-Al2O3The quality of particle is 18.0g, nm-TiO2
The quality of particle is 2.0g.
Step 3：Identical with the step of embodiment 1 three, difference is that shell raw material is Ca (CH3COO)2·H2O powder,
Ca (CH during heating and calcining3COO)2·H2O decomposes generation CaO as shell.
Embodiment 6CuO (66.4wt%)/CaO (13.6wt%)-TiO2(1wt%)-Al2O3(19wt%)
Step 1：It is identical with the step of embodiment 1 one.
Step 2：Identical with the step of embodiment 1 two, difference is, μm-Al2O3The quality of particle is 19.0g, nm-
TiO2The quality of particle is 1.0g, and the acid-base value of disperse system is adjusted with acetic acid and ammoniacal liquor.
Step 3：Identical with the step of embodiment 1 three, difference is first to add urea 83.6g as part of fuel, then
Add 38.4g Ca (CH3COO)2·H2O powder adds 201.7g Cu (NO as another part fuel3)2·3H2O crystal,
Wherein Cu (NO3)2·3H2O crystal and Ca (CH3COO)2·H2Raw material of the O powder as mixed active shell CuO/CaO.Screening
The particle size range gone out is 125 μm~300 μm, finally obtains required core-shell structure particles material, the material has CuO/CaO's
Shell is mixed, can be as burning chemistry chains and the combined cycle carrier of carbon dioxide absorption.
Embodiment 7CuO (66.4wt%)/CaO (13.6wt%)-MgO (5wt%)-Al2O3(15wt%)
Step 1：It is identical with the step of embodiment 3 one.
Step 2：Identical with the step of embodiment 3 two, difference is a μm-Al2O3The quality of particle is 15.0g, nm-MgO
The quality of particle is 5.0g.
Step 3：It is identical with the step of embodiment 6 three.
Embodiment 8NiO (15wt%)-TiO2(5wt%)-Al2O3(80wt%) catalyst
Step 1：It is identical with the step of embodiment 1 one.
Step 2：Identical with the step of embodiment 1 two, difference is no heating water bath, μm-Al2O3The quality of particle is
80.0g。
Step 3：Identical with the step of embodiment 1 three, difference is that shell raw material is Ni (NO3)2·6H2O crystal
58.4g, urea 20.1g.The particle size range screened out is 125 μm~180 μm, finally obtains required core-shell structure particles material
Material, the material can be as methane-CO 2 reformation or the catalyst of methane-steam reforming preparing synthetic gas.
Embodiment 9Pd (1wt%)-TiO2(10wt%)-Al2O3(89wt%) catalyst
Step 1：Identical with the step of embodiment 1 one, difference is to screen out α phases Al2O3Grain diameter is 1 μm~37 μ
m。
Step 2：Identical with the step of embodiment 1 two, difference is deionized water 50mL, without heating water bath, nm-
TiO2With a μm-Al2O3The quality of particle is respectively 1.0g and 8.9g.
Step 3：Identical with the step of embodiment 1 three, difference is that Shell Materials presoma is Pd (C2H3O2)2Powder
0.21g, do not add urea.The particle size range screened out is 75 μm~180 μm, finally obtains required core-shell structure particles material
Material, the material can be as the catalyst of catalytic burning organic waste gas.
Embodiment 10
Embodiment 2 is repeated with described same steps, difference is TiO2The particle diameter of particle is 1nm~100nm, and quality is
7g；Al2O3The particle diameter of particle is 75 μm~100 μm, quality 14g.
Embodiment 11
Embodiment 2 is repeated with described same steps, difference is TiO2The particle diameter of particle is 1nm~100nm, and quality is
7g；Al2O3The particle diameter of particle is 75 μm~100 μm, quality 14g.
Embodiment 12
Embodiment 2 is repeated with described same steps, difference is TiO2The particle diameter of particle is 1nm~100nm, and quality is
1g；Al2O3The particle diameter of particle is 75 μm~100 μm, quality 15g.
Embodiment 13
By the α phases Al that particle diameter is 37 μm~75 μm2O3Particle 17.5g is scattered in the deionized water in beaker, then adds urine
Cellulose crystal 97.5g is allowed to dissolve as fuel, adds Cu (NO3)2·3H2O crystal 235.4g is allowed to dissolve.Beaker is moved into
In air dry oven, after drying 24h under the conditions of 80 DEG C, core-shell structure particles material precursor is prepared；By the presoma
It is transferred in porcelain boat, porcelain boat then is put into the heating of Muffle furnace internal program lights and calcine；Muffle furnace sets 20 DEG C/min liter
Warm speed is heated to 950 DEG C from room temperature, and 2h is calcined at 950 DEG C, and product is annealed and cooled down, and grinding, screens out a diameter of 75 μm
~300 μm of particle, that is, obtain the core-shell structure copolymer Rotating fields granular materials of no interlayer.
Comparative example CuO (77.5wt%)-TiO2(5wt%)-Al2O3(17.5wt%) carrier of oxygen
Embodiment 1 is repeated with described same steps, distinguishes in step 2, is adjusted with dust technology or ammoniacal liquor scattered
The acid-base value of system, the pH value for making disperse system are 5.
Analysis of experimental results
The core prepared in the step 2 of the embodiment of the present invention 1-interlayer presoma is observed under transmission electron microscopy, can be seen
To nm-TiO2Particle uniformly coats μm-Al2O3Particle, as shown in Figure 4.
Core-shell structure particles material prepared by embodiment 1 is inlaid into epoxy resin, then mechanical polishing obtains particle
Cross section, the micro-structural of particle and the distribution of Cu, Ti, Al element are then observed under a scanning electron microscope, it can be found that
Obvious core shell structure, as shown in Figure 5.
The core-shell structure particles material prepared with same method to embodiment 2 is seen under a scanning electron microscope
Examine, and make a section among core-shell structure particles and carry out element distribution analysis (Fig. 6 a), it can be seen that Ca Elemental redistributions are in particle
Outermost layer (Fig. 6 b), Al Elemental redistributions are then distributed (Fig. 6 c) between the two layers in particle innermost layer (Fig. 6 d), Ti elements.
Circulation oxygen release-oxygen uptake performance of carrier of oxygen particle prepared by testing example 1 on thermogravimetric analyzer, due to pure
Cupric oxide oxygen release reacts：4CuO→2Cu2O+O2, the theoretical oxygen carrier rate that CuO can be calculated according to the chemical equation is 32/
(79.55 × 4) × 100%=10%, and because the mass fraction of active component CuO in the carrier of oxygen is 77.5%, therefore oxygen carries
The expectancy theory oxygen carrier amount of body is 77.5% × 10%=7.75%, and oxygen carrier amount is carried out on the basis of this expectancy theory oxygen carrier amount
Circulation experiment, as shown in Figure 7a, the oxygen carrier amount of the carrier of oxygen particle is close to ideal value, and performance base for 15 loop test results
This is without decaying.
The performance of the carrier of oxygen particle prepared with X-ray diffractometer to embodiment 1 and comparative example is tested.In Fig. 7 b
Three curve represents respectively, after the carrier of oxygen and 15 oxygen releases after the fresh carrier of oxygen that has just prepared, oxygen release-oxygen uptake circulation
The carrier of oxygen, it can be seen that the carrier of oxygen does not have CuAl during whole use2O4、CuAlO2Produce；And comparative example preparation is fresh
There is CuAl in the carrier of oxygen2O4Produce, as shown in Figure 7 c.
The CO that on thermogravimetric analyzer prepared by testing example 22The Cyclic Carbonation of absorbent-calcining performance, due to pure
Absorbent lime CO2React CaO+CO2→CaCO3, CaO CO can be calculated according to the chemical equation2Theoretical absorption rate is
44/56 × 100%=78%, and because the mass fraction of active component CaO in absorbent is 80%, therefore the expection of absorbent
Theoretical CO2Uptake is 80% × 78%=62%, 20 loop test results as shown in Figure 8 a, the CO2The absorption of absorbent is held
Amount close to ideal value, and after 20 circulations performance substantially without decaying.
The CO prepared with X-ray diffractometer to embodiment 22The performance of absorbent is tested, and two curves represent respectively,
The CO just prepared2CO after absorbent and 30 calcining-carb alphanatio pi cycles2Absorbent, it can be seen that CO2Absorbent is whole
There is no Ca during individual use12Al14O33、CaAl2O4、Ca3Al2O6Produce, as shown in Figure 8 b.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of core-shell structure particles material, it is characterised in that specific steps include：
Step 1：Nucleome material and interlayer material are dispersed in water, and it is pH ' to adjust pH value with acid or alkali, makes the nucleome
Material and the interlayer material fully assemble, to obtain the suspension of core-interlayer composite particles；
Wherein, the nucleome material be 1 μm~100 μm of particle diameter micron particles, the interlayer material be particle diameter be 1nm~
100nm nano particle, the mass ratio of the nucleome material and the interlayer material are more than or equal to 2:1, can be according to nucleome material
The thickness of the mass ratio of material and interlayer material control interlayer, reach the effect of controllable preparation interlayer；IEP1And IEP2It is respectively described
The isopotential point of nucleome material and the interlayer material, and IEP1With IEP2Difference be more than or equal to 2.5；PH ' is in IEP1And IEP2It
Between, and when pH value is pH ', the electrical opposite and difference of the Zeta potential of nucleome material and interlayer material is maximum；
Step 2：Metal nitrate and fuel are added into the suspension of step 1 is completely dissolved it, after fully drying
Calcined under anaerobic, finally grinding screening obtains required core-shell structure particles material, and the fuel is metal
Acetate；
It is also raw while metal nitrate and the fuel react generation metal oxide as shell completely in calcination process
Into nitrogen, vapor and carbon dioxide as accessory substance, the heat released using reaction can reduce the energy in calcination processing
Consumption, simultaneously effective reduce the pollutant NOx that nitrate decomposes release.
2. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that acid is vinegar described in step 1
Acid, hydrochloric acid or nitric acid, the alkali are ammoniacal liquor.
3. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that the nucleome material with it is described
The mass ratio of interlayer material is 3:1~15:1.
4. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that IEP1With IEP2Difference be more than
Equal to 5.
5. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that specifically include following steps：
Step 1：Screen out the α phases Al of 37 μm~75 μm of particle size range2O3Particle is standby, measures under different pH value aqueous conditions
Zeta potential so that determine particle isopotential point IEPA；Particle size range 10nm~100nm Rutile Type is chosen simultaneously
TiO2Nanoparticle sample, isopotential point IEP is determined with same methodT；
Step 2：300mL deionized waters are heated to 80 DEG C, then add μm-Al2O3Particle 15.0g stirs, and adds
nm-TiO2Particle 5.0g is uniformly mixed；The acid-base value of disperse system is adjusted with dust technology and ammoniacal liquor, makes the pH value of disperse system
For 6；
Step 3：Ca (CH are added into disperse system3COO)2·H2O powder 97.5g makes it fully molten as fuel, lasting stirring
Solution, adds Ca (NO3)2·4H2Raw materials of the O crystal 207.5g as shell, lasting stirring make it fully dissolve；In 80 DEG C of bars
After drying 24h under part, core-shell structure particles material precursor is prepared；2h is calcined at 950 DEG C and product is annealed and is cooled down,
Grinding, a diameter of 30 μm~300 μm of particle is screened out, that is, obtains required core-shell structure particles material, the material can conduct
CO2Absorbent.
6. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that specifically include following steps：
Step 1：Screen out the α phases Al of 37 μm~75 μm of particle size range2O3Particle is standby, measures under different pH value aqueous conditions
Zeta potential so that determine particle isopotential point IEPA；Particle size range 10nm~100nm Rutile Type is chosen simultaneously
TiO2Nanoparticle sample, isopotential point IEP is determined with same methodT；
Step 2：300mL deionized waters are heated to 80 DEG C, then add μm-Al2O3Particle 19g stirs, and adds nm-
TiO2Particle 1.0g is uniformly mixed；The acid-base value of disperse system is adjusted with acetic acid and ammoniacal liquor, the pH value for making disperse system is 6；
Step 3：Urea 83.6g is first added into disperse system as part of fuel, then adds 38.4g Ca (CH3COO)2·
H2O powder makes it fully dissolve, adds 201.7g Cu (NO as another part fuel, lasting stirring3)2·3H2O crystal,
Wherein Cu (NO3)2·3H2O crystal and Ca (CH3COO)2·H2Raw material of the O powder as mixed active shell CuO/CaO；80
After drying 24h under the conditions of DEG C, core-shell structure particles material precursor is prepared；2h is calcined at 950 DEG C, product is annealed cold
But, grind, screen out a diameter of 125 μm~300 μm of particle, that is, obtain required core-shell structure particles material, the material can
As burning chemistry chains and the combined cycle carrier of carbon dioxide absorption.
7. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that specifically include following steps：
Step 1：Screen out the α phases Al of 1 μm~37 μm of particle size range2O3Particle is standby, measures under different pH value aqueous conditions
Zeta potential so that determine particle isopotential point IEPA；Particle size range 10nm~100nm Rutile Type is chosen simultaneously
TiO2Nanoparticle sample, isopotential point IEP is determined with same methodT；
Step 2：μm-Al is added in 300mL deionized waters2O3Particle 1.0g stirs, and adds nm-TiO2Particle 8.9g
It is uniformly mixed, the acid-base value of disperse system is adjusted with dust technology and ammoniacal liquor, the pH value for making disperse system is 6；
Step 3：Pd (C are added into disperse system2H3O2)2For powder 0.21g as fuel, lasting stirring makes it fully dissolve, then adds
Enter Cu (NO3)2·3H2Raw materials of the O crystal 235.4g as shell, lasting stirring make it fully dissolve；Dried under the conditions of 80 DEG C
After 24h, core-shell structure particles material precursor is prepared；2h is calcined at 950 DEG C, and product is annealed and cooled down, is ground, sieve
A diameter of 75 μm~180 μm of particle is separated, that is, obtains required core-shell structure particles material, the material can be used as catalysis burning
The catalyst of organic exhaust gas.
8. the preparation method of core-shell structure particles material as claimed in claim 1, it is characterised in that metal nitrate and fuel are pressed
Stoichiometric proportion during according to complete reaction carries out dispensing.
A kind of 9. CO obtained using preparation method described in claim 52Absorbent, it is characterised in that：
The nucleome material is the α phases Al of 37 μm~75 μm particle diameters2O3Particle, the interlayer material are particle diameter 10nm~100nm's
Rutile Type TiO2Nano particle；The shell raw material is calcium acetate and calcium nitrate, and both mol ratios are 5:8.
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