CN106552624B - A kind of perovskite catalyst and its laser ablation preparation method and application - Google Patents
A kind of perovskite catalyst and its laser ablation preparation method and application Download PDFInfo
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- CN106552624B CN106552624B CN201610861762.XA CN201610861762A CN106552624B CN 106552624 B CN106552624 B CN 106552624B CN 201610861762 A CN201610861762 A CN 201610861762A CN 106552624 B CN106552624 B CN 106552624B
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
- Y02A50/2351—Atmospheric particulate matter [PM], e.g. carbon smoke microparticles, smog, aerosol particles, dust
Abstract
The invention discloses a kind of perovskite catalyst and its laser ablation preparation method and application, make easy to operation while not being influenced by pH using glucose as complexing agent by sol-gal process.It is sent using Rotary Evaporators rapid steaming and removes solvent instead of traditional long-time water bath with thermostatic control, then xerogel is prepared in drying in drying box, then obtains material requested through high-temperature calcination.The concentration for finally being improved oxide surface Lacking oxygen simultaneously using the quantity that liquid laser ablation increases active oxygen, is introduced active Lacking oxygen, increases catalytic activity, it realizes under diesel engine service condition, the direct oxidation of carbon soot particles reduces the discharge of particulate matter, reduces air pollution.
Description
Technical field
The present invention relates to new material technology field is belonged to, more specifically, it is related to a kind of synthesis of perovskite catalyst
Preparation method and application.
Background technique
Diesel engine is widely used because it has many advantages, such as that the thermal efficiency is high, fuel consumption rate is low and Power coverage is wide
In production and living.However the discharge amount of particulate matter is 30~70 times of gasoline engine in diesel engine vent gas, leads to serious air
With environmental pollution.The partial size of most of particulate matter can not only go deep into human respiratory tract less than 1 μm, and be enriched with a variety of nocuousness
The strong carcinogenic organic matter such as metal, polycyclic aromatic hydrocarbon, dioxin is very big to the health hazard of human body.Therefore, many countries all formulate
The discharge amount of increasingly strict emission regulation limitation diesel particulate.Currently, being difficult to by measure in the cylinders such as optimization burning
The requirement of stringent emission regulation, it is therefore desirable to meet increasingly strict discharge limitation using exhaust aftertreatment technology.
Particulate filter (DPF) be it is generally acknowledged at present it is most effective reduce diesel particulate discharge post-processing technology it
One.The technology eliminates exhaust particulate by the way of physical filtering.With the deposition of particulate matter, pressure drop is increased, engine power
It is reduced with fuel economy, it is necessary to which burning purification is carried out to realize the regeneration of DPF to the particulate matter of deposition.In general, soot
The thermodynamics oxidizing temperature of particulate matter is up to 600 DEG C, and the delivery temperature of diesel vehicle is between 200~500 DEG C, lower row
Temperature degree is difficult to make carbon soot particles directly by O2Oxidizing fire.The activation energy of oxygen can be effectively reduced in oxidation catalyst, to drop
The ignition temperature of low-carbon cigarette.Therefore, oxidation catalyst coating, that is, CDPF is introduced in DPF, realizes diesel engine truck exhaust temperature strip
It is one of the important means of granular material discharged to become effectively removing diesel vehicle for the direct oxidation of carbon soot particles under part.Noble metal is to bavin
The oxidation of oil machine exhaust carbon fume particulate matter has excellent catalytic properties, but since its is at high cost, resistance to SO_2 is poor, and activity
The disadvantages of being mutually easy sintering or volatilization at high temperature, limits noble metal catalyst in China's diesel particulate to a certain extent
The application of field of purification.Some alternative catalysts such as transition metal oxide, alkali metal oxide, perofskite type oxide with
And cerium base oxide relies on many advantages, such as low in cost, chemical stability is good, thermal stability is high, arranges in catalytic eliminating diesel engine
Play the part of important role in terms of soot particulate in gas.
Perofskite type oxide (ABO3) in the types of B metal ions determine redox characteristic and the catalysis of oxide
Activity, and A ions mainly play a part of the skeleton and rock-steady structure of photocatalyst crystals, are made by the collaboration of A, B metals
With influence perovskite material catalytic activity, at the same time, by precious metal doping can further increase its catalytic activity and
Sulfur resistive ability.Although however, living by the catalysis that the means such as doping, increasing specific surface area improve RE perovskite oxide
Property, the initiation temperature of soot or higher.Compared to the oxygen to dissociate in air, the active oxygen of oxide surface chemisorption is in carbon
Show superior activity in the oxidation of smoke particle object, and the concentration and biography of the quantity of active oxygen and oxide surface Lacking oxygen
It passs closely related.Therefore, the Lacking oxygen of oxide surface and its supply action are effectively regulated and controled, is to improve catalyst to urge
Change one of activity, the effective means for reducing the discharge of diesel emission particulate object.Using the alkali or alkaline earth metal element of low price
Part replaces the chemical valence of the A bit usually modulation B bit element in perovskite structure, or use transition metal element part to take
It is the main method for increasing perovskite oxide surface Lacking oxygen for B bit element.However the oxygen that the method for lattice substitution introduces is empty
Site concentration is limited.Another common approach is to be heat-treated under vacuum or reducing atmosphere to catalysis material, this
Method needs the conditions such as high temperature and pressure, is unfavorable for being mass produced, and there is presently no effective methods to control Lacking oxygen
Concentration.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, the perovskite catalyst for overcoming existing synthetic method to obtain
The disadvantage that thermal stability is poor, specific surface area is smaller, catalytic activity is low is sintered the side for then using superlaser ablation using gel
Method substantially increases the thermal stability and catalytic activity of catalyst, further promotes the development of automotive exhaust catalysis research.Liquid
Phase laser ablation method, directly by solid powder physical crushing, can not only improve Specific Surface Area Measurement using superlaser, and
A large amount of Lacking oxygens can be introduced on the surface of oxide particle, substantially increase the catalytic activity of catalyst.The present invention uses high energy
The laser treatment RE perovskite oxide of amount, broad pulse introduces active Lacking oxygen, increases catalytic activity, realizes in diesel engine
Under service condition, the direct oxidation of carbon soot particles reduces the discharge of particulate matter, reduces the pollution of atmosphere.
Technical purpose of the invention is achieved by following technical proposals:
A kind of perovskite catalyst and its laser ablation preparation method, perovskite catalyst chemical expression are La (Pt/
Pd)xMn1-xO3, wherein x is 0.1-0.4, is prepared as steps described below
Step 1, it is matched according to perovskite catalyst chemical expression, by lanthanum nitrate (La (NO3)3·6H2) and second O
Sour manganese (C4H6MnO4·4H2O it) is sufficiently impregnated in xerogel platinum/palladium (Pt/Pd) mixed solution prepared, in which: platinum/palladium mixing
Solution is molten to be directly dissolved in chloroazotic acid obtained platinum/palladium (Pt/Pd) mixing using the platinum of 20 mass fractions and the palladium of 80 mass fractions
Liquid, platinum/palladium mixed solution dosage are 6-24 mass fractions；Use the lanthanum nitrate (La (NO of 57-62 mass fractions3)3·
6H2) and the manganese acetate (C of 6-24 mass fractions O4H6MnO4·4H2O it) is add to deionized water wiring solution-forming, is added into solution
Entering glucose makes the molar ratio 1:1 of metal ion (i.e. the sum of lanthanoid metal and manganese metal) Yu glucose, and total metal ion
Concentration is 0.01mol/L, will be transferred in revolving instrument and is rotated to coagulation glue is obtained after above-mentioned solution ultrasonic disperse, dry be made is done
Gel；
When carrying out xerogel preparation, revolving temperature is 60-80 degrees Celsius, preferably 60-70 degrees Celsius.
When carrying out xerogel preparation, revolving is transferred to the obtained xerogel of 80 DEG C of dry 12h in crucible after obtaining coagulation glue.
Step 2, it will be sintered in Muffle furnace after the gel drying after step 1 dipping, with the rate of 3-5 DEG C/min from room
20-25 degrees Celsius of temperature is increased to 400-500 DEG C, keeps 2-4h of temperature, decomposes the nitrate in presoma completely, then with
The rate of 8-10 DEG C/min is increased to 800-850 DEG C, calcines 3-5h, then cools to 20 DEG C~25 DEG C of room temperature with the furnace, finally
Obtain perovskite catalyst.
It in step 2, is air atmosphere in Muffle furnace.
In step 2, at 400-450 DEG C, 2-3h of temperature is kept, decomposes the nitrate in presoma completely；?
800-820 DEG C, calcine 3-4h.
Step 3, in water by perovskite catalyst ultrasonic disperse, it is located on the water surface with laser and exports millisecond pulse
Laser signal carries out ablation to perovskite catalyst, after the reaction was completed washs product to neutral and dry, millisecond pulse laser
Signal parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms, 1-10HZ of frequency, wavelength 523nm, 150-350mJ/ of energy
cm2, for laser target surface apart from 5-10mm of the water surface, the ablation time is 30-60min；
In step 3, for laser target surface apart from 5-6mm of the water surface, the ablation time is 50-60min.
In step 3, millisecond pulse laser signal parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms, frequency 5-
10HZ, wavelength 523nm, 200-300mJ/cm of energy2。
The present invention handles catalyst using liquid laser ablation, laser action sample by the interaction with sample,
Lacking oxygen can be increased, while introducing active oxygen, increase the specific surface area of catalyst.To increase connecing for catalyst and particulate matter
Contacting surface product, improves the rate of release of active oxygen, and the increase of Lacking oxygen quantity can reinforce the oxygen storage capacity and and raising oxygen of catalyst
Change reducing property, thus the raising catalytic activity of sample.Before and after liquid laser ablation processes, specific surface area of catalyst becomes
Change, it is untreated substantially in 9-12m2/ g, it is processed in 40-50m2/g。
Compared with prior art, the CO catalytic oxidation performance of sample prepared by the present invention and NO catalytic oxidation performance exist
LaMnO3The sample that method after doping using laser ablation obtains improves for the catalytic performance of CO and NO, sample
The beginning conversion temperature of product CO and NO are about 200 DEG C (200-250 degrees Celsius average), are urged compared to what sol-gal process obtained
Agent catalytic performance improves.Further explanation is doped to perovskite and carries out laser ablation processing for urging
The performance of agent improves a lot, i.e. the application in catalytic eliminating diesel exhaust gas in soot particulate.
Detailed description of the invention
Fig. 1 is the TEM photo of sample prepared by the present invention.
Fig. 2 is the HRTEM photo of sample prepared by the present invention.
Fig. 3 is the electron diffraction diagram of sample prepared by the present invention.
Fig. 4 is the uv-visible absorption spectroscopy figure of sample prepared by the present invention.
Fig. 5 is the XRD spectra of sample prepared by the present invention.
Fig. 6 is the sample NO catalysis oxidation that embodiment one in the present invention, embodiment two, embodiment three, example IV obtain
Performance test figure.
Fig. 7 is the sample CO catalysis oxidation that embodiment one in the present invention, embodiment two, embodiment three, example IV obtain
Performance test figure.
Specific embodiment
Technical solution of the present invention is further illustrated below with reference to specific implementation case, wherein lanthanum nitrate, manganese acetate, grape
Sugar recovers fine chemistry industry research institute purchased from Tianjin, and deionized water, platinum, palladium are purchased from University Of Tianjin Ke Wei company, hydrochloric acid, and nitric acid is purchased from
One factory of Tianjin chemical reagent.According to 20:80 mass parts ratio being directly dissolved in chloroazotic acid using platinum and palladium, to prepare platinum/palladium (Pt/Pd) mixed
Close solution carry out using, directly weighed in embodiment platinum/palladium (Pt/Pd) mixed solution use.Proportion is according to La (Pt/Pd)xMn1-xO3The parameter of x is matched in perovskite catalyst.As x=0.1,62.02 parts (mass fraction) of lanthanum nitrate (La is taken
(NO3)3·6H2O), 31.58 parts of manganese acetate (C4H6MnO4·4H2O) and 6.4 parts platinum/palladium (Pt/Pd) mixed solution proportion；
As x=0.2,60.28 parts of lanthanum nitrate (La (NO is taken3)3·6H2O), 27.28 parts of manganese acetate (C4H6MnO4·4H2O) and
12.44 parts of platinum/palladium (Pt/Pd) mixed solution proportion；As x=0.3,58.63 parts of (lanthanum nitrate (La (NO are taken3)3·
6H2O), 23.22 parts of manganese acetate (C4H6MnO4·4H2O) and 18.15 parts platinum/palladium (Pt/Pd) mixed solution proportion；Work as x=
When 0.4,57.07 parts of lanthanum nitrate (La (NO is taken3)3·6H2O), 19.37 parts of manganese acetate (C4H6MnO4·4H2) and 23.56 O
Platinum/palladium (Pt/Pd) mixed solution proportion of part, embodiment specific as follows.
Embodiment one:
12.99g lanthanum nitrate (La (NO is weighed in the balance according to element chemistry metering ratio in catalyst chemical formula3)3·
6H2O), 6.625g manganese acetate (C4H6MnO4·4H2O it) is dissolved in 600mL deionized water and is made into metal ion total concentration and is
Then 10.8g glucose is added in the solution of 0.1mol/L into mixed solution, stir to uniformly mixed.Then mixed liquor is existed
It is evaporated (60 DEG C) on Rotary Evaporators, until forming honey shape wet gel, is then transferred to wet gel in crucible in an oven
80 DEG C (air atmosphere) dry 12h obtain fluffy, frangible, faint yellow xerogel；
Above-mentioned gained xerogel is sufficiently impregnated in platinum/palladium (Pt/Pd) mixed solution containing 1.3404g；
400 DEG C are warming up under Muffle furnace air atmosphere with 3 DEG C/min and 2h is kept to keep the nitrate in presoma complete
It decomposes, then 10 DEG C/min is warming up to 800 DEG C of calcining 3h and perovskite catalyst is made.
Catalyst is placed on ultrasound 1h in 30ml deionized water, the parameter of laser (millisecond pulse laser) are as follows: power
106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength 523nm, energy 350mJ/cm2, laser target surface is apart from liquid level
5mm acts on 50min, is after the reaction was completed centrifuged products therefrom to solution to neutral with ethyl alcohol under the rate of 4000r/min,
By 8~10h dry at 60 DEG C of product obtained.
It can see by electron diffraction diagram in attached drawing, the crystallinity of obtained sample is good, the ring-type of diffraction spot in figure
Structure is more regular, still contains perovskite structure in powder, and doping and the introducing of laser do not have an impact the structure of perovskite,
The crystalline size that can see sample from TEM photo is 30-50nm, the crystal ruler obtained compared to traditional sol-gal process
It is very little, it is smaller using the crystal powder size after laser ablation.By the lattice constant for observing the available product of HRTEM photo
About 0.447nm (0.44-0.45nm of average out to), obtained product have the preferable uniformity and ideal regular pattern.
It can be seen that the range of the absorption peak for the sample that laser ablation obtains in 600- by the ultraviolet-visible absorption map in attached drawing
900nm, it is consistent with the absorption peak position of perovskite-type compounds.Peak in figure difference can see by XRD spectra in attached drawing
Corresponding LaMn1-xO3Characteristic peak, respectively correspond (110) of crystal, (112), (202), (220), (310), (024), (224),
(420) crystal face, and corresponding characteristic peak is due to caused by doping Pt/Pd, although peak intensity is smaller, but still can at " * "
To observe, show to be successfully prepared La (Pt/Pd)xMn1-xO3Perovskite catalyst, and crystal phase is more pure.
Embodiment two
12.99g lanthanum nitrate (La (NO is weighed in the balance according to element chemistry metering ratio in catalyst chemical formula3)3·
6H2O), 5.880g manganese acetate (C4H6MnO4·4H2O it) is dissolved in 600mL deionized water and is made into metal ion total concentration and is
Then 10.8g glucose is added in the solution of 0.1mol/L into mixed solution, stir to uniformly mixed.Then mixed liquor is existed
It is evaporated (60 DEG C) on Rotary Evaporators, until forming honey shape wet gel, is then transferred to wet gel in crucible in an oven
80 DEG C (air atmosphere) dry 12h obtain fluffy, frangible, faint yellow xerogel；
Above-mentioned gained xerogel is sufficiently impregnated in platinum/palladium (Pt/Pd) mixed solution containing 2.6808g；
400 DEG C are warming up under Muffle furnace air atmosphere with 3 DEG C/min and 2h is kept to keep the nitrate in presoma complete
It decomposes, then 10 DEG C/min is warming up to 800 DEG C of calcining 3h and perovskite catalyst is made.
Catalyst is placed on ultrasound 1h in 30ml deionized water, the parameter of laser (millisecond pulse laser) are as follows: power
106w/cm2, voltage 720v, pulsewidth 10ms, frequency 5Hz, wavelength 523nm, energy 300mJ/cm2, laser target surface is apart from liquid level
5mm acts on 50min, is after the reaction was completed centrifuged products therefrom to solution to neutral with ethyl alcohol under the rate of 4000r/min,
By 8~10h dry at 60 DEG C of product obtained.
Embodiment three
12.99g lanthanum nitrate (La (NO is weighed in the balance according to element chemistry metering ratio in catalyst chemical formula3)3·
6H2O), 5.145g manganese acetate (C4H6MnO4·4H2O it) is dissolved in 600mL deionized water and is made into metal ion total concentration and is
Then 10.8g glucose is added in the solution of 0.1mol/L into mixed solution, stir to uniformly mixed.Then mixed liquor is existed
It is evaporated (60 DEG C) on Rotary Evaporators, until forming honey shape wet gel, is then transferred to wet gel in crucible in an oven
80 DEG C (air atmosphere) dry 12h obtain fluffy, frangible, faint yellow xerogel；
Above-mentioned gained xerogel is sufficiently impregnated in platinum/palladium (Pt/Pd) mixed solution containing 4.0212g；
400 DEG C are warming up under Muffle furnace air atmosphere with 3 DEG C/min and 2h is kept to keep the nitrate in presoma complete
It decomposes, then 10 DEG C/min is warming up to 800 DEG C of calcining 3h and perovskite catalyst is made.
Catalyst is placed on ultrasound 1h in 30ml deionized water, the parameter of laser (millisecond pulse laser) are as follows: power
106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength 523nm, energy 150mJ/cm2, laser target surface is apart from liquid level
6mm acts on 30min, is after the reaction was completed centrifuged products therefrom to solution to neutral with ethyl alcohol under the rate of 4000r/min,
By 8~10h dry at 60 DEG C of product obtained.
Example IV
12.99g lanthanum nitrate (La (NO is weighed in the balance according to element chemistry metering ratio in catalyst chemical formula3)3·
6H2O), 4.410g manganese acetate (C4H6MnO4·4H2O it) is dissolved in 600mL deionized water and is made into metal ion total concentration and is
Then 10.8g glucose is added in the solution of 0.1mol/L into mixed solution, stir to uniformly mixed.Then mixed liquor is existed
It is evaporated (60 DEG C) on Rotary Evaporators, until forming honey shape wet gel, is then transferred to wet gel in crucible in an oven
80 DEG C (air atmosphere) dry 12h obtain fluffy, frangible, faint yellow xerogel；
Above-mentioned gained xerogel is sufficiently impregnated in platinum/palladium (Pt/Pd) mixed solution containing 5.3616g；
400 DEG C are warming up under Muffle furnace air atmosphere with 3 DEG C/min and 2h is kept to keep the nitrate in presoma complete
It decomposes, then 10 DEG C/min is warming up to 800 DEG C of calcining 3h and perovskite catalyst is made.
Catalyst is placed on ultrasound 1h in 30ml deionized water, the parameter of laser (millisecond pulse laser) are as follows: power
106w/cm2, voltage 720v, pulsewidth 10ms, frequency 10Hz, wavelength 523nm, energy 200mJ/cm2, laser target surface is apart from liquid level
10mm acts on 60min, is after the reaction was completed centrifuged products therefrom to solution to neutral with ethyl alcohol under the rate of 4000r/min,
By 8~10h dry at 60 DEG C of product obtained.
Specific test equipment model and parameter are as follows: (1) XRD: the Rigaku D/MAX 2500v/pc of Rigaku production
Model X-ray diffractometer (Cu target,Under 40KV tube voltage, 100mA tube current operating condition) to sample
It is tested.Scanning speed is 5 °/min, and surface sweeping range is 10 ° -80 °；(2) the TECNAI G of FEI Co. of U.S. output2-F20
Type Flied emission transmission electron microscope carries out phenetic analysis, acceleration voltage 200KV to sample.Sample be after ultrasonic disperse,
It hangs on copper mesh in advance, is put into transmission electron microscope later and carries out observation analysis；(3) active shadow of the catalyst for particulate matter
Sound is carried out on temperature programming adsorption/desorption instrument (ChemBET Pulsar TPD/TPR).Experimental procedure are as follows: weigh 50mg
Sample is placed on quartzy bottom of the tube, gets lodged in quartz ampoule both ends with a small amount of mineral wool, guarantees catalyst while guaranteeing that ventilation is smooth
It is not blown out by gas.400 DEG C are warming up to from room temperature with 5 DEG C/min in the atmosphere of He, 30min is kept the temperature at 400 DEG C, is then dropped
Temperature arrives room temperature, is switched to 10%O2Or 10%O2The atmosphere (30ml/min) of+500ppmNO is from 50 DEG C with 10 DEG C/min heating
To 700 DEG C, and the LC-D200 on-line mass spectroscopy instrument detector recording CO produced with AMETEK company2、CO、NO、NO2The variation of concentration
Situation；(4) UV-2550 Shimadzu ultraviolet-uisible spectrophotometer is used, powder sample is packed into sample cell, in wavelength 200-
Analysis is scanned in the range of 2600nm wavelength.
Using characteristic temperature TmAs the characteristic temperature point for measuring catalyst activity, reacted by being plotted in catalysis
CO in journey2Concentration variation curve, choose sample CO2It is most fast that the highest point of peak concentration, i.e. carbon dioxide generate rate
Point, corresponding temperature is as characteristic temperature Tm, characteristic temperature TmIt is lower, indicate that sample gets over the catalytic activity of soot particulate
It is good.In CO catalytic oxidation performance test chart, embodiment one and embodiment three play peak temperature at 200 DEG C, and characteristic temperature is at 300 DEG C
With 310 DEG C；Embodiment two and embodiment rise from all around peak temperature at 300 DEG C, and characteristic temperature is coagulated in 400 DEG C and 440 DEG C compared to colloidal sol
The atmosphere temperature and characteristic temperature for the catalyst that glue method obtains have apparent reduction.Illustrate to be doped perovskite and swash
Photoengraving processing improves a lot for the performance of catalyst.Using characteristic temperature TmAs measurement catalyst activity
Characteristic temperature point, by being plotted in NO in catalytic reaction process2Concentration variation curve, choose sample NO2Peak concentration highest
Point, i.e. carbon dioxide generates the most fast point of rate, and corresponding temperature is as characteristic temperature Tm, characteristic temperature TmIt is lower, indicate sample
Product are better for the catalytic activity of soot particulate.In NO catalytic oxidation performance test chart, embodiment one and embodiment three are risen
Peak temperature is at 200 DEG C, and characteristic temperature is in 300 DEG C and 305 DEG C；Embodiment two and embodiment rise from all around peak temperature at 300 DEG C, feature temperature
The atmosphere temperature and characteristic temperature for the catalyst that degree is obtained in 410 DEG C and 460 DEG C, compared to sol-gal process have apparent drop
It is low.Further explanation is doped and is carried out to perovskite laser ablation processing and improves a lot for the activity of catalyst.
The adjustment that component and technique are carried out according to the method that the content of present invention is recorded, can prepare corresponding catalyst, and
Show the performance almost the same with above-described embodiment.Illustrative description has been done to the present invention above, it should explanation,
In the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art can not be spent
The equivalent replacement of expense creative work each falls within protection scope of the present invention.
Claims (6)
1. a kind of perovskite catalyst, which is characterized in that perovskite catalyst chemical expression is La (Pt/Pd)xMn1-xO3,
Middle x is 0.1-0.4, specific surface area 40-50m2/ g, is prepared as steps described below:
Step 1, it is matched according to perovskite catalyst chemical expression, xerogel prepared by lanthanum nitrate and manganese acetate is existed
It is sufficiently impregnated in platinum/palladium mixed solution, in which: platinum/palladium mixed solution is the platinum and 80 mass fractions using 20 mass fractions
Palladium, which is directly dissolved in chloroazotic acid, is made platinum/palladium mixed solution, and platinum/palladium mixed solution dosage is 6-24 mass fractions；Use 57-
The manganese acetate of the lanthanum nitrate of 62 mass fractions and 6-24 mass fractions is add to deionized water wiring solution-forming, adds into solution
Entering glucose makes the molar ratio 1:1 of metal ion and glucose, and the concentration of total metal ion is 0.01mol/L, will be above-mentioned
It is transferred in revolving instrument and is rotated to coagulation glue is obtained after solution ultrasonic disperse, xerogel is made in drying；
Step 2, it will be sintered in Muffle furnace after the gel drying after step 1 dipping, with the rate of 3-5 DEG C/min from room temperature
20-25 degrees Celsius are increased to 400-500 DEG C, keep 2-4h of temperature, decompose the nitrate in presoma completely, then with 8-
The rate of 10 DEG C/min is increased to 800-850 DEG C, calcines 3-5h, then cools to room temperature with the furnace, finally obtain perovskite and urge
Agent；
Step 3, in water by perovskite catalyst ultrasonic disperse, it is located on the water surface with laser and exports millisecond pulse laser
Signal carries out ablation to perovskite catalyst, after the reaction was completed washs product to neutral and dry, millisecond pulse laser signal
Parameter is power 106w/cm2, voltage 720v, pulsewidth 10ms, 1-10Hz of frequency, wavelength 523nm, 150-350mJ/cm of energy2,
For laser target surface apart from 5-10mm of the water surface, the ablation time is 30-60min.
2. a kind of perovskite catalyst according to claim 1, which is characterized in that when carrying out xerogel preparation, revolving
Temperature is 60-80 degrees Celsius；Revolving is transferred to the obtained xerogel of 80 DEG C of dry 12h in crucible after obtaining coagulation glue.
3. a kind of perovskite catalyst according to claim 1, which is characterized in that when carrying out xerogel preparation, revolving
Temperature is 60-70 degrees Celsius；Revolving is transferred to the obtained xerogel of 80 DEG C of dry 12h in crucible after obtaining coagulation glue.
4. a kind of perovskite catalyst according to claim 1, which is characterized in that be air in Muffle furnace in step 2
Atmosphere keeps 2-3h of temperature, decomposes the nitrate in presoma completely at 400-450 DEG C；At 800-820 DEG C, calcining
3—4h。
5. a kind of perovskite catalyst according to claim 1, which is characterized in that in step 3, laser target surface distance
5-6mm of the water surface, ablation time are 50-60min, and millisecond pulse laser signal parameter is power 106w/cm2, voltage 720v, arteries and veins
Wide 10ms, 5-10Hz of frequency, wavelength 523nm, 200-300mJ/cm of energy2。
6. application of the perovskite catalyst as described in claim 1 in catalytic eliminating diesel exhaust gas in soot particulate.
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