CN108714426A - A kind of nanocube perovskite type catalyst and its preparation method and application - Google Patents
A kind of nanocube perovskite type catalyst and its preparation method and application Download PDFInfo
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- CN108714426A CN108714426A CN201810623417.1A CN201810623417A CN108714426A CN 108714426 A CN108714426 A CN 108714426A CN 201810623417 A CN201810623417 A CN 201810623417A CN 108714426 A CN108714426 A CN 108714426A
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- nitrate
- perovskite type
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- nanocube
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 40
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 29
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 29
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 15
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 14
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 14
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 6
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000004615 ingredient Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 9
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IRPDISVJRAYFBI-UHFFFAOYSA-N nitric acid;potassium Chemical compound [K].O[N+]([O-])=O IRPDISVJRAYFBI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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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
- B01J23/70—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- 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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/61—Surface area
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention belongs to purifying vehicle exhaust catalysis technical fields, and in particular to a kind of nanocube La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst and its preparation method and application.The present invention is using manganese carbonate as presoma, using sodium nitrate and potassium nitrate as fused salt, sodium nitrate, potassium nitrate, lanthanum nitrate, strontium nitrate, manganese carbonate and copper nitrate are uniformly mixed, calcined after grinding, calcined product is washed, after drying, obtains nanocube perovskite type catalyst.The present invention is with precipitation method synthesis of cubic body MnCO3, and for the first time with cube MnCO3For presoma, nanocube perovskite type catalyst is synthesized under lower temperature using molten-salt growth method, the catalyst preparation period is short, preparation flow is simple to operation, at low cost, and stability is good, it is 90% (T to have higher low-temperature catalytic activity, CO conversion ratios to the CO ingredients in vehicle exhaust90) and 50% (T50) temperature significantly reduce.
Description
Technical field
The invention belongs to purifying vehicle exhaust catalysis technical fields, and in particular to a kind of nanocube
La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst and its preparation method and application.
Background technology
Vehicle exhaust is one of main source of air pollution at present, and the pollutant in vehicle exhaust includes mainly NOx、
CO2, CO, hydro carbons, aldehydes, lead, sulfide etc., wherein CO is that content highest is maximum to human injury in automobile exhaust pollution object
Therefore gas for environmental protection, ensures that health, Air Pollution prevention and control, processing vehicle exhaust become urgently to be resolved hurrily and ask
Topic.
Currently, most auto-exhaust catalyst that come into operation is noble metal catalyst, using noble metal as raw material system
Standby catalyst, though low temperature active is high, high temperature active and stability are poor, and resources reserve is few, of high cost, and then limit
The development of noble metal catalyst.And perovskite type catalyst, because its catalytic performance is excellent, structural stability is good, and manufacturing cost is low,
It is expected to replace current expensive noble metal catalyst in future.
Currently, the preparation method of traditional perovskite catalyst is numerous, such as solid phase method, sol-gal process, citric acid network
It is legal etc., but these preparation methods calcination temperature is high, and long preparation period, the sample specific surface area of acquisition are low.Therefore, one is prepared
Kind of calcination temperature is low, short preparation period and manufacturing cost it is low high activated catalyst it is particularly important.
Compared to the perovskite catalyst of no special appearance, cube perovskite type catalyst shows superior catalysis
Active and high stability.Currently, the technology of preparing about cube perovskite catalyst rarely has report.
Invention content
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of nanocube La0.6Sr0.4Mn0.8Cu0.203
Perovskite type catalyst and its preparation method and application.
For achieving the above object, the technical solution adopted in the present invention is：
A kind of nanocube La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst, molecular formula are
La0.6Sr0.4Mn0.8Cu0.203。
A kind of nanocube La0.6Sr0.4Mn0.8Cu0.203The preparation method of perovskite type catalyst, including walk as follows
Suddenly：
(1) molten-salt growth method is used, with MnCO3For presoma and manganese source, with NaNO3And KNO3For fused salt, by sodium nitrate, nitric acid
Potassium, lanthanum nitrate, strontium nitrate, manganese carbonate and copper nitrate are uniformly mixed, and are first ground, are subsequently placed in Muffle furnace and calcine；
(2) calcining terminates after being cooled to room temperature, and calcined product is scattered in deionized water, and 45 DEG C~55 DEG C stirring 2h~
3h, then after being washed repeatedly with deionized water and absolute ethyl alcohol, be placed in 60 DEG C~70 DEG C drying 8h~10h, obtain nanocube
La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst.
In said program, the lanthanum nitrate, strontium nitrate, manganese carbonate and copper nitrate molar ratio are 0.6:0.4:0.8:0.2.
In said program, the amount of the substance of the fused salt and the lanthanum nitrate, strontium nitrate, manganese carbonate and copper nitrate total material
Amount ratio be 5.
In said program, the molar ratio of the sodium nitrate and potassium nitrate is 1.5.
In said program, the calcination temperature is 550 DEG C~750 DEG C, and heating rate is 4 DEG C/min, soaking time 2h
~6h.More preferably scheme, the calcination temperature are 550 DEG C~650 DEG C, and heating rate is 4 DEG C/min, soaking time 2h
~6h.
In said program, the manganese carbonate is cube manganese carbonate.
In said program, the cube manganese carbonate is prepared via a method which to obtain：By manganese sulfate and sodium bicarbonate point
It is not dissolved in deionized water, is quickly poured into manganese sulfate solution after the two is completely dissolved, then by sodium bicarbonate solution, 12h is stirred
~13h stands 2h~3h, after being washed repeatedly with deionized water and absolute ethyl alcohol, is placed in 60 DEG C~70 DEG C drying 8h~10h and obtains
Cube MnCO3。
The molar ratio of the manganese sulfate and sodium bicarbonate is 1:1.
Above-mentioned nanocube La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is as CO catalyst in vehicle exhaust
The application of purifying and catalyzing technical field.
Beneficial effects of the present invention：The present invention is for the first time with precipitation method synthesis of cubic body MnCO3, and with cube MnCO3It is preceding
Body is driven, nanocube La has been synthesized under lower temperature using molten-salt growth method0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst,
Low temperature synthesis condition is conducive to the raising of specific surface area, and the catalyst preparation period is short, and preparation flow is simple to operation, cost
Low, stability is good, has higher low-temperature catalytic activity to the CO ingredients in vehicle exhaust；In the present invention, the A of perovskite catalyst
Position and the B strontium ions and copper ion for being doped with optimal proportion respectively, increase the lattice defect and Lacking oxygen of catalyst, make vapour
CO conversion ratios are 90% (T in tail gas90) and conversion ratio be 50% (T50) temperature significantly reduce, this also illustrates the catalysis
Agent shows excellent low-temperature catalytic activity to the CO ingredients in vehicle exhaust.
Description of the drawings
Fig. 1 is cube MnCO prepared by the present invention3XRD spectrum.
Fig. 2 is cube MnCO prepared by the present invention3FE-SEM collection of illustrative plates, wherein Fig. 2 (a) engineer's scales be 2 μm, Fig. 2 (b)
Engineer's scale is 200nm.
Fig. 3 is cube MnCO prepared by the present invention3FE-TEM collection of illustrative plates, engineer's scale be 0.5 μm.
Fig. 4 is nanocube La prepared by Examples 1 to 50.6Sr0.4Mn0.8Cu0.203The XRD of perovskite type catalyst
Collection of illustrative plates.
Fig. 5 is nanocube La prepared by embodiment 10.6Sr0.4Mn0.8Cu0.203The FE-SEM of perovskite type catalyst
Collection of illustrative plates, engineer's scale 100nm.
Fig. 6 is nanocube La prepared by embodiment 10.6Sr0.4Mn0.8Cu0.203The FE-TEM of perovskite type catalyst
Collection of illustrative plates, engineer's scale 50nm.
Fig. 7 is nanocube La prepared by Examples 1 to 50.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is to CO's
Catalyzed conversion activity curve.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
In following embodiment, the cube MnCO3Presoma is made by the steps to obtain：Take two 2000ml clean
Net beaker pours into the deionized water of 630ml respectively, later by 0.1512g MnSO4·H2O and 0.7560g NaHCO3It is molten respectively
Sodium bicarbonate solution after the two is completely dissolved, is quickly poured into sulfuric acid by solution in two beakers equipped with 630ml deionized waters
In manganese solution, after being stirred 12 hours under room temperature, 2h is stood, precipitation is filtered to take, with 1000ml deionized waters and the anhydrous second of 300ml
Alcohol washs repeatedly, precipitated product dry 8h in 70 DEG C of insulating boxs, you can obtain cube MnCO3。
Prepare gained cube MnCO3XRD spectrum as shown in Figure 1, pure phase can be prepared by the precipitation method as shown in Figure 1
Diamond shape MnCO3(JCPDS No.44-1472, R-3c, a=0.47901nm, c=1.5694nm).The cube MnCO3FE-
SEM spectrum is as shown in Figure 2, it is known that the MnCO prepared3For the cube that surface is smooth.The cube MnCO3FE-TEM figure
Spectrum is as shown in Figure 3, it is known that the MnCO prepared3For solid cube.
Embodiment 1
Nanocube La0.6Sr0.4Mn0.8Cu0.203 perovskite type catalyst is prepared via a method which to obtain：It weighs
The cube MnCO of 0.036mol lanthanum nitrates and the above-mentioned preparations of 0.048mol3, 0.024mol strontium nitrates, 0.012mol copper nitrates,
The raw material weighed is uniformly mixed and is ground in mortar, then pours into 5ml earthenwares by 0.36mol sodium nitrate, 0.24mol potassium nitrate
It in crucible, is finally placed in Muffle furnace, is raised to 550 DEG C from room temperature with the rate of 4 DEG C/min, keeps the temperature 2h at this temperature, then with furnace cooling
But arrive room temperature, the product of calcining is scattered in deionized water, and with 2h is stirred at 50 DEG C, then spend 1000ml ionized waters and
300ml absolute ethyl alcohols wash repeatedly after in insulating box 70 DEG C of dry 8h can be obtained the nanocube
La0.6Sr0.4Mn0.8Cu0.203 perovskite type catalyst.
The present embodiment prepares gained cube La0.6Sr0.4Mn0.8Cu0.203The XRD spectrum of perovskite type catalyst such as Fig. 4
It is shown, as can be seen from Figure 4, with cube MnCO3For presoma, using La made from molten-salt growth method0.6Sr0.4Mn0.8Cu0.203Perovskite
Type catalyst is analogous to a cube LaMn03The calcium Qin Kuang phases of (JCPDS No.75-440, Pm-3m, a=0.388nm).This implementation
The example cube La0.6Sr0.4Mn0.8Cu0.203The FE-SEM collection of illustrative plates of perovskite type catalyst is as shown in figure 5, as can be seen from Figure 5
La0.6Sr0.4Mn0.8Cu0.203The microscopic appearance of perovskite type catalyst is nanocube.Cube described in the present embodiment
La0.6Sr0.4Mn0.8Cu0.203The FE-TEM collection of illustrative plates of perovskite type catalyst is as shown in fig. 6, as can be seen from Figure 6, it is known that
La0.6Sr0.4Mn0.8Cu0.203 perovskite type catalyst is really nanocube.
To cube La obtained in the present embodiment0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst carries out CO catalysis and turns
Change active testing, steps are as follows：
Mixed gas composition is set as 5vol%O by simulated automotive tail gas2, 2vol%CO, 93vol%Ar, total flow is
438ml/min air speeds are 12000h-1；There are the 0.25g silica wools of 0.1g catalyst to be fitted into the quartz ampoule of a diameter of 8mm load
Portion, quartz ampoule are positioned over again on miniature fixed quartzy bed reactor；Tube furnace heats sample, and heated perimeter is 75 DEG C~300
DEG C, temperature interval is 25 DEG C, and in gas chromatograph fid detector is detected the gas after reaction, determines sample to CO
Catalyzed conversion performance.Test results are shown in figure 7, it is known that the catalyst activity is higher, and CO conversion ratios reach at 87.00 DEG C
To 50% (T50=87 DEG C), when temperature reaches 97.67, CO conversion ratios have just reached 90% (T90=97.67 DEG C), thus say
Bright, which shows excellent low-temperature catalytic activity to the CO ingredients in vehicle exhaust.
Embodiment 2
The present embodiment prepares nanocube La0.6Sr0.4Mn0.8Cu0.203The step of perovskite type catalyst and embodiment 1
It is roughly the same, the difference is that：Calcination temperature is 650 DEG C.
Cube La manufactured in the present embodiment0.6Sr0.4Mn0.8Cu0.203The XRD spectrum of perovskite type catalyst such as Fig. 4 institutes
Show, is a cube LaMn0 as can be seen from Figure 43(JCPDS No.75-440, Pm-3m, a=0.388nm) calcium Qin Kuang phases.This implementation
Cube La prepared by example0.6Sr0.4Mn0.8Cu0.203Catalyzed conversion active testing step and reality of the perovskite type catalyst to CO
It is identical to apply example 1, as shown in Figure 7, the present embodiment prepares gained La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is 113.73
DEG C when, CO conversion ratios have just reached 50% (T50=112.73 DEG C), the conversion ratio when temperature reaches 123.89 DEG C just reaches
90% (T90=123.89. DEG C), thus illustrate, which shows the CO ingredients in vehicle exhaust excellent low-temperature catalyzed
Activity.
Embodiment 3
The present embodiment prepares nanocube La0.6Sr0.4Mn0.8Cu0.203The step of perovskite type catalyst and embodiment 1
It is roughly the same, the difference is that：Calcination temperature is 750 DEG C.
Cube La manufactured in the present embodiment0.6Sr0.4Mn0.8Cu0.203The XRD spectrum of perovskite type catalyst such as Fig. 4 institutes
Show, is a cube LaMn0 as can be seen from Figure 43(JCPDS No.75-440, Pm-3m, a=0.388nm) calcium Qin Kuang phases.This implementation
Cube La prepared by example0.6Sr0.4Mn0.8Cu0.203Catalyzed conversion active testing step and reality of the perovskite type catalyst to CO
It is identical to apply example 1, as shown in Figure 7, the present embodiment prepares gained La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is 161.47
DEG C when, CO conversion ratios have just reached 50% (T50=161.47 DEG C), the conversion ratio when temperature reaches 173.14 DEG C just reaches
90% (T100=173.14 DEG C), thus illustrate, which shows preferable low temperature to the CO ingredients in vehicle exhaust and urge
Change activity.
Embodiment 4
The present embodiment prepares nanocube La0.6Sr0.4Mn0.8Cu0.203The step of perovskite type catalyst and embodiment 1
It is roughly the same, the difference is that：Soaking time is 4h.
Cube La manufactured in the present embodiment0.6Sr0.4Mn0.8Cu0.203The XRD spectrum of perovskite type catalyst such as Fig. 4 institutes
Show, is a cube LaMn0 as can be seen from Figure 43(JCPDS No.75-440, Pm-3m, a=0.388nm) calcium Qin Kuang phases.This implementation
Cube La prepared by example0.6Sr0.4Mn0.8Cu0.203Catalyzed conversion active testing step and reality of the perovskite type catalyst to CO
It is identical to apply example 1, as shown in Figure 7, the present embodiment prepares gained La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is 111.37
DEG C when, CO conversion ratios have just reached 50% (T50=111.37 DEG C), when temperature reaches 122.35 DEG C, conversion ratio reaches 90%
(T90=122.35 DEG C), thus illustrate, which shows the CO ingredients in vehicle exhaust excellent low-temperature catalyzed work
Property.
Embodiment 5
The present embodiment prepares nanocube La0.6Sr0.4Mn0.8Cu0.203The step of perovskite type catalyst and embodiment 1
It is roughly the same, the difference is that：Soaking time is 6h.
Cube La manufactured in the present embodiment0.6Sr0.4Mn0.8Cu0.203The XRD spectrum of perovskite type catalyst such as Fig. 4 institutes
Show, is a cube LaMn0 as can be seen from Figure 43(JCPDS No.75-440, Pm-3m, a=0.388nm) calcium Qin Kuang phases.This implementation
Cube La prepared by example0.6Sr0.4Mn0.8Cu0.203Catalyzed conversion active testing step and reality of the perovskite type catalyst to CO
It is identical to apply example 1, as shown in Figure 7, the present embodiment prepares gained La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst is 112.73
DEG C when, CO conversion ratios have just reached 50% (T50=112.73 DEG C), when temperature is 123.03 DEG C, conversion ratio has just reached 90%
(T90=123.03 DEG C), thus illustrate, which shows excellent low-temperature catalytic activity to the CO ingredients in vehicle exhaust.
Obviously, above-described embodiment be only intended to clearly illustrate made by example, and not limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection domain of the invention.
Claims (10)
1. a kind of nanocube perovskite type catalyst, which is characterized in that the nanocube perovskite type catalyst
Molecular formula is La0.6Sr0.4Mn0.8Cu0.203。
2. the preparation method of nanocube perovskite type catalyst described in claim 1, which is characterized in that including walking as follows
Suddenly：
（1）Using molten-salt growth method, with MnCO3For presoma and manganese source, with NaNO3And KNO3For fused salt, by sodium nitrate, potassium nitrate, nitre
Sour lanthanum, strontium nitrate, manganese carbonate and copper nitrate are uniformly mixed, and are first ground, are subsequently placed in Muffle furnace and calcine；
（2）Calcining terminates after being cooled to room temperature, and calcined product is scattered in deionized water, 45 DEG C ~ 55 DEG C stirring 2h ~ 3h, then
After being washed repeatedly with deionized water and absolute ethyl alcohol, 60 DEG C ~ 70 DEG C drying 8h ~ 10h are placed in, nanocube is obtained
La0.6Sr0.4Mn0.8Cu0.203Perovskite type catalyst.
3. preparation method according to claim 2, which is characterized in that the lanthanum nitrate, strontium nitrate, manganese carbonate and copper nitrate
Molar ratio is 0.6:0.4:0.8:0.2.
4. preparation method according to claim 2, which is characterized in that the amount of the substance of the fused salt and the lanthanum nitrate,
The ratio of the amount of strontium nitrate, manganese carbonate and copper nitrate total material is 5.
5. preparation method according to claim 2, which is characterized in that the molar ratio of the sodium nitrate and potassium nitrate is 1.5.
6. preparation method according to claim 2, which is characterized in that the calcination temperature is 550 DEG C ~ 750 DEG C, heating speed
Rate is 4 DEG C/min, and soaking time is 2h ~ 6h.
7. preparation method according to claim 6, which is characterized in that the calcination temperature is 550 DEG C ~ 650 DEG C, heating speed
Rate is 4 DEG C/min, and soaking time is 2h ~ 6h.
8. preparation method according to claim 2, which is characterized in that the manganese carbonate is cube manganese carbonate.
9. preparation method according to claim 7, which is characterized in that the cube manganese carbonate is prepared via a method which
It obtains：Manganese sulfate and sodium bicarbonate are dissolved in deionized water respectively, after the two is completely dissolved, then sodium bicarbonate solution is quick
It pours into manganese sulfate solution, stirs 12h ~ 13h, stand 2h ~ 3h and be placed in 60 after being washed repeatedly with deionized water and absolute ethyl alcohol
DEG C ~ 70 DEG C drying 8h ~ 10h obtain cube MnCO3。
10. nanocube perovskite type catalyst described in claim 1 is catalyzed skill as CO catalyst in purifying vehicle exhaust
The application in art field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038557A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院海洋研究所 | A kind of electro-catalysis GOx/MnCO3Composite material and its preparation and application |
| CN110292935A (en) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof |
| CN112058270A (en) * | 2020-06-16 | 2020-12-11 | 武汉理工大学 | Flaky La0.8Sr0.2CoO3In-situ synthesis method and application of perovskite catalyst |
| CN112429777A (en) * | 2020-11-02 | 2021-03-02 | 广西科技大学 | Perovskite-like structure solid material and preparation thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02288159A (en) * | 1989-04-28 | 1990-11-28 | Ngk Insulators Ltd | Ceramic electrode and fuel cell having same |
| JPH07136518A (en) * | 1993-11-22 | 1995-05-30 | Nissan Motor Co Ltd | Exhaust gas purifying catalyst |
| CN101274215A (en) * | 2007-12-27 | 2008-10-01 | 清华大学 | Rare earth perovskite type oxygen storage material for purifying vehicle tail gas |
| US7585474B2 (en) * | 2005-10-13 | 2009-09-08 | The Research Foundation Of State University Of New York | Ternary oxide nanostructures and methods of making same |
| CN101748487A (en) * | 2009-12-11 | 2010-06-23 | 广东工业大学 | Method for preparing single crystal perovskite type oxide and application thereof |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN105107520A (en) * | 2015-07-21 | 2015-12-02 | 新奥科技发展有限公司 | Double perovskite type metal oxide catalyst and preparation method thereof |
| CN106238066A (en) * | 2016-07-29 | 2016-12-21 | 武汉理工大学 | A kind of spherical porous perovskite type catalyst La0.4sr0.6mn0.8fe0.2o3and its preparation method and application |
-
2018
- 2018-06-15 CN CN201810623417.1A patent/CN108714426B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02288159A (en) * | 1989-04-28 | 1990-11-28 | Ngk Insulators Ltd | Ceramic electrode and fuel cell having same |
| JPH07136518A (en) * | 1993-11-22 | 1995-05-30 | Nissan Motor Co Ltd | Exhaust gas purifying catalyst |
| US7585474B2 (en) * | 2005-10-13 | 2009-09-08 | The Research Foundation Of State University Of New York | Ternary oxide nanostructures and methods of making same |
| CN101274215A (en) * | 2007-12-27 | 2008-10-01 | 清华大学 | Rare earth perovskite type oxygen storage material for purifying vehicle tail gas |
| CN101748487A (en) * | 2009-12-11 | 2010-06-23 | 广东工业大学 | Method for preparing single crystal perovskite type oxide and application thereof |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN105107520A (en) * | 2015-07-21 | 2015-12-02 | 新奥科技发展有限公司 | Double perovskite type metal oxide catalyst and preparation method thereof |
| CN106238066A (en) * | 2016-07-29 | 2016-12-21 | 武汉理工大学 | A kind of spherical porous perovskite type catalyst La0.4sr0.6mn0.8fe0.2o3and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 吕春玲等: ""亚微米碳酸锰的制备及表征"", 《中北大学学报（自然科学版）》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110292935A (en) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof |
| CN110038557A (en) * | 2019-05-20 | 2019-07-23 | 中国科学院海洋研究所 | A kind of electro-catalysis GOx/MnCO3Composite material and its preparation and application |
| CN110038557B (en) * | 2019-05-20 | 2022-02-11 | 中国科学院海洋研究所 | Electrocatalysis GOx/MnCO3Composite material, preparation and application thereof |
| CN112058270A (en) * | 2020-06-16 | 2020-12-11 | 武汉理工大学 | Flaky La0.8Sr0.2CoO3In-situ synthesis method and application of perovskite catalyst |
| CN112058270B (en) * | 2020-06-16 | 2023-05-23 | 武汉理工大学 | Flaky La 0.8 Sr 0.2 CoO 3 In-situ synthesis method and application of perovskite catalyst |
| CN112429777A (en) * | 2020-11-02 | 2021-03-02 | 广西科技大学 | Perovskite-like structure solid material and preparation thereof |
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