CN107497443A - Automotive exhaust catalysis nano material and preparation method thereof - Google Patents
Automotive exhaust catalysis nano material and preparation method thereof Download PDFInfo
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- CN107497443A CN107497443A CN201710835351.8A CN201710835351A CN107497443A CN 107497443 A CN107497443 A CN 107497443A CN 201710835351 A CN201710835351 A CN 201710835351A CN 107497443 A CN107497443 A CN 107497443A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 32
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(III) nitrate Inorganic materials [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 27
- 239000004071 soot Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of tail gas catalyzed nano material La0.3K0.7Co1‑XNiXO3Preparation method.The inventive method is with La (NO3)3•6H2O、KNO3、Co(NO3)3•6H2O and Ni (NO3)3•6H2O is raw material, and citric acid is complexing agent, and La is prepared using sol-gal process0.3K0.7Co1‑xNixO3Presoma；Presoma obtains tail gas catalyzed material La by calcining0.3K0.7Co1‑xNixO3.The inventive method raw material are easy to get, preparation technology compared with it is simple, product granularity is uniform, catalytic activity is high, quality is good and high-temperature stability is good, there is excellent industrial utilization prospect in terms of exhaust carbon-smoke particulate catalytic.
Description
Technical field
The present invention relates to auto-exhaust catalyst field, and in particular to a kind of tail gas catalyzed nano material and its preparation side
Method.
Background technology
In recent years, as China's rapid development of economy, automobile largely enter family, brought convenience to people's trip same
When, serious pollution is also generated, wherein, the soot particulate contained in the tail gas of discharge is air PM2.5 main source
One of, and a kind of serious carcinogen, carry out serious threat to environment and the health care belt of the people.Nowadays, Environmental
Protection problem pay attention to day by day, reducing atmosphere pollution and PM2.5 discharge capacitys and having become environmental administration must face and urgently to be resolved hurrily
Major issue.
Perovskite composite oxide, formula ABO3, A positions or B positions are substituted or portion by other elements in perovskite structure
Unique texture and the composite oxides of performance are synthesized after dividing substitution, so as to form the B positions ion of anion defect or different valence state.
Research shows, as long as the tolerance factor t of perovskite（, wherein rA、rB、 rORespectively A, B and
The ionic radius of O positions）Between 0.75~1.0, the structure of perovskite can keep certain stability, and this is provided to the composition of perovskite
Some flexibilities, exactly perofskite type oxide material have this special structure so that perovskite-type material have air-sensitive,
The characteristic such as electrical conductance and catalytic activity.
In catalytic field, since Libby proposed that perovskite composite oxide had good exhaust fume catalytic in 1971
Since performance, many researchs are carried out to this, it is intended to the sufficiently expensive precious metal catalyst of Ca-Ti ore type compound fictitious hosts
Agent.But existing such material is still barely satisfactory in the effect of soot particulate processing application, it would be highly desirable to improves or exploitation is new
Description of materials.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of technique it is relatively simple, without large-scale special installation, product granularity
Uniformly, measured tail gas catalyzed nano material of matter and preparation method thereof.
In order to solve the above technical problems, present invention employs following technical research route：
Keeping perovskite ABO3In the case that structure is constant, using cobalt acid lanthanum based perovskite A ions and B ions by it is other from
Subdivision modulation is modified, i.e., using K+Instead of the La of part A positions3+, using Ni3+Instead of part B positions Co3+（Different B positions ion
With A positions ion while direct modulation）, to produce the defects of more, improve and improve its redox ability, and then height is prepared
The perovskite oxide of catalytic efficiency；Having abandoned traditional has limitation Research approach（The valence state and oxidation-reduction quality of B positions ion
Can be with the performance of the metal ion of substitution A positions ion and substitution amount etc.）.
Concrete technical scheme is as follows：
A kind of tail gas catalyzed nano material is designed, its chemical general formula is La0.3K0.7Co1-XNiXO3, wherein x=0.1~0.9.
The preparation method of the tail gas catalyzed nano material, comprises the following steps：
（1）Weigh solid La (NO3) 3•6H2O、KNO3、Co(NO3) 3•6H2O and Ni (NO3) 3•6H2O, respectively plus distilled water is matched somebody with somebody
Corresponding nitrate solution is made；
（2）According to the nonstoichiometric molar ratio of the tail gas catalyzed nano material, step is measured respectively（1）The nitrate solution
Add in container, the container for filling mixed solution is then kept into constant temperature, citric acid solution is slowly added in sonic oscillation, so
After be maintained at water bath with thermostatic control until forming gelinite A；
（3）The gelinite A is placed in convection oven powder is obtained after heat drying, precursor B is obtained after grinding；
（4）The precursor B is placed in electric furnace and calcined, is naturally cooling to room temperature, produces tail gas catalyzed nano material
La0.3K0.7Co1-X NiXO3。
Preferably, the step（1）The concentration control of middle nitrate solution is 0.05~1.0mol L-1。
Preferably, the step（2）The temperature control of middle constant temperature is 70~80 DEG C.
Preferably, the step（2）Described in the concentration of citric acid solution be 1.0mol L-1。
Preferably, the step（2）In press citric acid：Metal ion=1.1~2.0:1 mol ratio adds the lemon
Acid solution.
Preferably, the step（3）Middle heat drying temperature control is 100~110 DEG C.
Preferably, the step（4）Middle calcining heat control is 500~700 DEG C.
Preferably, the step（4）Middle calcination time control is 2~4h.
Compared with prior art, advantageous effects of the invention are：
1. the present invention is by ABO3A positions and B positions simultaneously direct modulation, i.e., using K+Instead of part La3+, B positions use Ni3+
Part substitutes Co3+, synthesis defect is more, specific surface area is big, particle is uniformly distributed, the tail gas catalyzed nano material of excellent catalytic effect.
It is 2. the raw materials used wide material sources of the present invention, cheap；Method technique is simple, without large-scale special expensive equipment,
Simple operation, investment is small, is easy to industrialized production.
3. the product granularity of the present invention is uniform, average grain diameter is 30~45nm, and high catalytic efficiency, high-temperature stability is good, tool
There is excellent prospects for commercial application.
Brief description of the drawings
Fig. 1 is tail gas catalyzed nano material La0.3K0.7Co0.9Ni0.1O3X-ray diffraction XRD spectrum；
Fig. 2 is tail gas catalyzed nano material La0.3K0.7Co0.7Ni0.3O3X-ray diffraction XRD spectrum；
Fig. 3 is tail gas catalyzed nano material La0.3K0.7Co0.3Ni0.7O3X-ray diffraction XRD spectrum；
Fig. 4 is tail gas catalyzed nano material La0.3K0.7Co0.1Ni0.9O3X-ray diffraction XRD spectrum；
In figure, y-axis represents relative intensity, generally omits.
Embodiment
Illustrate the embodiment of the present invention with reference to the accompanying drawings and examples, but following examples are used only in detail
Describe the bright present invention in detail, the scope not limiting the invention in any way.
Involved instrument and equipment is routine instrument device unless otherwise instructed in the examples below；Involved
Raw material and reagent are commercially available conventional products unless otherwise instructed；Involved detection or method of testing, unless otherwise instructed,
It is conventional method.
Embodiment 1：
A kind of tail gas catalyzed nano material La0.3K0.7Co0.9Ni0.1O3Preparation method, comprise the following steps：
（1）Precise 21.6500g La (NO3) 3•6H2O, 5.055g KNO3, 14.5535g Ni (NO3) 3•6H2O、
14.5395g Co (NO3) 3•6H2It is 0.5mol L that O, which is separately added into deionized water and is configured to ion concentration,-1Solution.
（2）According to La0.3K0.7Co0.9Ni0.1O3The requirement of middle nonstoichiometric molar ratio, the step of taking certain amount respectively
（1）La (the NO of resulting solution, i.e. 90ml3)3The KNO of solution, 210ml3Ni (the NO of solution, 30ml3) 3The Co of solution, 270ml
(NO3) 3•6H2O solution, add in container, it is 70~80 DEG C of thermostatted waters that the container for filling mixed solution then is put into temperature
Bath, 450ml 1.0mol L are then slowly added in sonic oscillation-1Citric acid solution, mixed after sonic oscillation 20min
Solution A1。
（3）By gelinite A1It is placed in convection oven after heat drying under the conditions of 100~110 DEG C and obtains
La0.3K0.7Co0.9Ni0.1O3Powder, precursor B is obtained after grinding1。
（4）By precursor B1It is placed in electric furnace, calcines 3h under the conditions of 700 DEG C, be naturally cooling to room temperature, produces tail gas and urge
Change nano material La0.3K0.7Co0.9Ni0.1O3。
Embodiment 2：
Tail gas catalyzed nano material La0.3K0.7Co0.9Ni0.1O3X-ray diffraction：Produced using Dutch PANalytical companies
X'pert Pro types x-ray powder diffraction instruments carry out analyze catalysis material phase composition, operating voltage 30kV, electric current 30mA,
Using CuK α （λ=0.1540598nm）As radiographic source.
Gained nano material La0.3K0.7Co0.9Ni0.1O3X ray diffracting spectrum（XRD）As shown in figure 1, it can therefrom see
Go out, material purity is high, and average grain diameter is 40~50nm.
Embodiment 3：
Tail gas catalyzed nano material La0.3K0.7Co0.9Ni0.1O3Catalytic combustion activity analysis：
（1）Soot simulated automotive exhaust carbon-smokes particle is taken as control, purchased from German Printex, soot average grain diameters 25nm；
（2）By material La0.3K0.7Co0.9Ni0.1O3With soot with mass ratio position 15:Mixed after 1 ratio grinding 10-60 min
Close sample；
（3）The sample is taken in simultaneous synthesis heat analysis TG/DSC（NETZSCH STA409PC/PG）Carry out testing soot most on device
Temperature Tm corresponding to large-scale combustion speed, heating rate are 10 DEG C/min.
As a result show, compared with being not added with catalyst, add nano material La0.3K0.7Co0.9Ni0.1O3The maximum combustions of soot can be made
Burn rate temperature Tm and be down to 365~372 DEG C from about 590 DEG C, Catalytic Combustion Effect is notable.
Embodiment 4：
A kind of tail gas catalyzed nano material La0.3K0.7Co0.7Ni0.3O3Preparation method, comprise the following steps：
（1）Precise 2.1650g La (NO3) 3•6H2O, 5.055g KNO3, 14.5535g Ni (NO3) 3•6H2O、
14.5395g Co (NO3) 3•6H2It is 0.05mol L that O, which is separately added into deionized water and is configured to ion concentration,-1Solution.
（2）According to La0.3K0.7Co0.7Ni0.3O3The requirement of middle nonstoichiometric molar ratio, the step of taking certain amount respectively
（1）La (the NO of resulting solution, i.e. 30ml3)3The KNO of solution, 210ml3Ni (the NO of solution, 90ml3) 3The Co of solution, 210ml
(NO3) 3•6H2O solution, add in container, it is 70~80 DEG C of thermostatted waters that the container for filling mixed solution then is put into temperature
Bath, 60ml 1.0mol L are then slowly added in sonic oscillation-1Citric acid solution, mixed after sonic oscillation 10min
Solution A2。
（3）By gelinite A2It is placed in convection oven after heat drying under the conditions of 100~110 DEG C and obtains
La0.3K0.7Co0.7Ni0.3O3Powder, precursor B is obtained after grinding2。
（4）By precursor B2It is placed in electric furnace, calcines 4h under the conditions of 500 DEG C, be naturally cooling to room temperature, produces a nanometer material
Expect La0.3K0.7Co0.7Ni0.3O3。
Embodiment 5：
As described in Example 2, tail gas catalyzed nano material La is tested0.3K0.7Co0.7Ni0.3O3X-ray diffraction, collection 2θFrom 6 °
Data in the range of 90 °, gained nano material La0.3K0.7Co0.7Ni0.3O3XRD spectrum as shown in Fig. 2 can therefrom see
Go out, material purity is high, and average grain diameter is 25~35nm.
Embodiment 6：
As described in Example 3, tail gas catalyzed nano material La is analyzed0.3K0.7Co0.7Ni0.3O3Catalytic combustion activity, as a result show
Show, compared with being not added with catalyst, add nano material La0.3K0.7Co0.7Ni0.3O3Can make soot maximum combustion rate temperature Tm from
About 590 DEG C are down to 360~368 DEG C, and Catalytic Combustion Effect is notable.
Embodiment 7：
A kind of tail gas catalyzed nano material La0.3K0.7Co0.3Ni0.7O3Preparation method, comprise the following steps：
（1）Precise 433.0000g La (NO3) 3•6H2O, 101.1000g KNO3, 291.0700g Ni (NO3) 3•
6H2O, 290.7900g Co (NO3) 3•6H2It is 1.0mol L that O, which is separately added into deionized water and is configured to ion concentration,-1Solution.
（2）According to La0.3K0.7Co0.3Ni0.7O3The requirement of middle nonstoichiometric molar ratio, the step of taking certain amount respectively
（1）La (the NO of resulting solution, i.e. 45ml3)3The KNO of solution, 105ml3Ni (the NO of solution, 105ml3) 3The Co of solution, 45ml
(NO3) 3•6H2O solution, add in container, it is 70~80 DEG C of thermostatted waters that the container for filling mixed solution then is put into temperature
Bath, 330ml 1.0mol L are then slowly added in sonic oscillation-1Citric acid solution, mixed after sonic oscillation 30min
Solution A3。
（3）By gelinite A3It is placed in convection oven after heat drying under the conditions of 100~110 DEG C and obtains
La0.3K0.7Co0.3Ni0.7O3Powder, precursor B is obtained after grinding3。
（4）By precursor B3It is placed in electric furnace, calcines 4h under the conditions of 600 DEG C, be naturally cooling to room temperature, produces a nanometer material
Expect La0.3K0.7Co0.3Ni0.7O3。
Embodiment 8：
As described in Example 2, tail gas catalyzed nano material La is tested0.3K0.7Co0.3Ni0.7O3X-ray diffraction, collection 2θFrom 6 °
Data in the range of 90 °, gained nano material La0.3K0.7Co0.3Ni0.7O3XRD spectrum as shown in figure 3, can therefrom see
Go out, material purity is high, and average grain diameter is 30~40nm.
Embodiment 9：
As described in Example 3, tail gas catalyzed nano material La is analyzed0.3K0.7Co0.3Ni0.7O3Catalytic combustion activity, as a result show
Show, compared with being not added with catalyst, add nano material La0.3K0.7Co0.3Ni0.7O3Can make soot maximum combustion rate temperature Tm from
About 590 DEG C are down to 334~346 DEG C, and Catalytic Combustion Effect is notable.
Embodiment 10：
A kind of tail gas catalyzed nano material La0.3K0.7Co0.1Ni0.9O3Preparation method, comprise the following steps：
（1）Precise 43.3000g La (NO3) 3•6H2O, 101.1000g KNO3, 291.0700g Ni (NO3) 3•
6H2O, 290.7900g Co (NO3) 3•6H2It is 1.0mol L that O, which is separately added into deionized water and is configured to ion concentration,-1Solution.
（2）According to La0.3K0.7Co0.1Ni0.9O3The requirement of middle nonstoichiometric molar ratio, the step of taking certain amount respectively
（1）La (the NO of resulting solution, i.e. 45ml3)3The KNO of solution, 105ml3Ni (the NO of solution, 135ml3) 3The Co of solution, 15ml
(NO3) 3•6H2O solution, add in container, it is 70~80 DEG C of thermostatted waters that the container for filling mixed solution then is put into temperature
Bath, 330ml 1.0mol L are then slowly added in sonic oscillation-1Citric acid solution, mixed after sonic oscillation 30min
Solution A4。
（3）By gelinite A4It is placed in convection oven after heat drying under the conditions of 100~110 DEG C and obtains
La0.3K0.7Co0.1Ni0.9O3Powder, precursor B is obtained after grinding4。
（4）By precursor B4It is placed in electric furnace, calcines 2h under the conditions of 600 DEG C, be naturally cooling to room temperature, produces a nanometer material
Expect La0.3K0.7Co0.1Ni0.9O3。
Embodiment 11：
As described in Example 2, tail gas catalyzed nano material La is tested0.3K0.7Co0.1Ni0.9O3X-ray diffraction, collection 2θFrom 6 °
Data in the range of 90 °, gained nano material La0.3K0.7Co0.1Ni0.9O3XRD spectrum as shown in figure 4, can therefrom see
Go out, material purity is high, and average grain diameter is 30~40nm.
Embodiment 12：
As described in Example 3, tail gas catalyzed nano material La is analyzed0.3K0.7Co0.1Ni0.9O3Catalytic combustion activity, as a result show
Show, compared with being not added with catalyst, add nano material La0.3K0.7Co0.1Ni0.9O3Can make soot maximum combustion rate temperature Tm from
About 590 DEG C are down to 338~345 DEG C, and Catalytic Combustion Effect is notable.
In summary embodiment and the tail gas catalyzed nano material catalysis burning of the long-term practical studies analysis present invention is combined
The reason for significant effect, essentially consists in：
（1）The A positions of material of the present invention are using the relatively large K of part low price, radius+Displacement high price, the less La of radius3+,
On the one hand, the release of active cells oxygen is accelerated, and caused Lacking oxygen and can is adsorbed and activation gas phase O2, and burnt in soot
Accelerate the movement of oxygen species in reaction, and then improve catalytic efficiency；
（2）In order to keep electroneutral, the increase of B positions cation valence, Co3+、Ni3+Improve to Co part4+、Ni4+, or form oxygen sky
Cave, high price Co4+、Ni4+Cation, which exists, causes the oxidation activity of perovskite further to improve, so as to reduce Soot burnings
Temperature.
The present invention is described in detail above in conjunction with drawings and examples, still, those of skill in the art
Member can also be carried out it is understood that on the premise of present inventive concept is not departed to each design parameter in above-described embodiment
Change, forms multiple specific embodiments, is the common excursion of the present invention, is no longer described in detail one by one herein.
Claims (9)
1. a kind of automotive exhaust catalysis nano material, it is characterised in that its chemical general formula is La0.3K0.7Co1-XNiXO3, wherein x=
0.1~0.9.
2. the preparation method of the automotive exhaust catalysis nano material described in claim 1, it is characterised in that comprise the following steps：
（1）Weigh solid La (NO3) 3•6H2O、KNO3、Co(NO3) 3•6H2O and Ni (NO3) 3•6H2O, respectively plus distilled water is matched somebody with somebody
Corresponding nitrate solution is made；
（2）According to the tail gas catalyzed nano material La0.3K0.7Co1-XNiXO3Nonstoichiometric molar ratio, measure step respectively
（1）The nitrate solution mixing, is slowly added to citric acid solution in the following sonic oscillation side of constant temperature, then keeps constant temperature
Until form gelinite A；
（3）The gelinite A is placed in after heat drying and obtains powder, precursor B is obtained after grinding；
（4）The precursor B is calcined, is naturally cooling to room temperature,.
3. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（1）
In, the concentration control of nitrate solution is 0.05~1.0mol L-1。
4. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（2）
In, the temperature control of constant temperature is 70~80 DEG C.
5. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（2）
In, the concentration of the citric acid solution is 1.0mol L-1。
6. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（2）
In, by citric acid：Metal ion=1.1~2.0:1 mol ratio adds the citric acid solution.
7. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（3）
In, heat drying temperature control is 100~110 DEG C.
8. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（4）
In, calcining heat control is 500~700 DEG C.
9. the preparation method of tail gas catalyzed nano material according to claim 2, it is characterised in that in the step（4）
In, calcination time control is 2~4h.
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