CN112337461A - Strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite, preparation method and application in catalytic oxidation of toluene - Google Patents
Strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite, preparation method and application in catalytic oxidation of toluene Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 132
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 title claims description 41
- 238000001354 calcination Methods 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
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- 239000000463 material Substances 0.000 claims abstract description 12
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract 7
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002603 lanthanum Chemical class 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 150000002940 palladium Chemical class 0.000 claims description 8
- 159000000008 strontium salts Chemical class 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
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- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 33
- 239000007789 gas Substances 0.000 abstract description 11
- 229910052712 strontium Inorganic materials 0.000 abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011572 manganese Substances 0.000 abstract description 7
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002071 nanotube Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 abstract 1
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- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 abstract 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 11
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- 238000003917 TEM image Methods 0.000 description 6
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- 239000003513 alkali Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 2
- 229910004416 SrxMnO3 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 229910002578 La0.2Sr0.8MnO3 Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 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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- 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
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Abstract
本发明公开了一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用，以La(NO3)3·6H2O,Mn(NO3)2,Sr(NO3)2作为镧源、锰源、锶源，以硅模板分子筛作为硬模板，以柠檬酸作为络合剂，通过蒸发、干燥、煅烧、氢氧化钠溶液刻蚀得到La1‑ xSrxMnO3纳米管材料；取La1‑xSrxMnO3作为载体，加入氯钯酸钠金属前驱体，通过搅拌溶剂热蒸发以及氢气还原煅烧得到负载钯的La1‑xSrxMnO3纳米管复合材料。本发明Pd@La1‑xSrxMnO3复合材料中锶的引入增加了四价锰的含量从而促进甲苯的催化氧化，实现了在较低温度下的高效催化氧化甲苯，对降解工业生产、生活中所排放的污染气体甲苯有很好的应用前景。
The invention discloses a strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material, a preparation method and an application in catalytic oxidation of toluene. La(NO 3 ) 3 ·6H 2 O, Mn(NO 3 ) 2 , Sr(NO 3 ) 2 is used as lanthanum source, manganese source and strontium source, silicon template molecular sieve is used as hard template, citric acid is used as complexing agent, and it is obtained by evaporation, drying, calcination and etching with sodium hydroxide solution. La 1- x Sr x MnO nanotube material; take La 1 - x Sr x MnO as carrier, add sodium chloropalladate metal precursor, obtain La 1-x supported palladium by stirring solvothermal evaporation and hydrogen reduction calcination Sr x MnO 3 nanotube composites. The introduction of strontium in the Pd@La 1-x Sr x MnO 3 composite material of the present invention increases the content of tetravalent manganese so as to promote the catalytic oxidation of toluene, realizes high-efficiency catalytic oxidation of toluene at a relatively low temperature, and is beneficial to the degradation of industrial production, Toluene, a polluting gas emitted in life, has a good application prospect.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium, a preparation method thereof and application thereof in catalytic oxidation of toluene.
Background
Volatile Organic Compounds (VOCs) are important precursors for causing atmospheric composite pollution such as urban haze and photochemical pollution, have great influence on human health and ecological environment, and have attracted wide attention of governments and the public. At present, the processing methods for VOCs mainly comprise: adsorption, absorption, membrane separation, plasma, photocatalysis, catalytic oxidation, and the like. The catalytic oxidation method is widely applied due to low operation temperature, high efficiency and low energy consumption, and the core problem of the method is to develop and research a catalyst with low temperature, high activity, good thermal stability and low price. Noble metal catalysts have been widely studied for their excellent catalytic properties, but since noble metals are easily agglomerated and undergo deactivation during application, a stable support having a large surface area is required to support the noble metal materials.
The perovskite oxide is rich in reserve and has good redox capacity, the surface area of the perovskite oxide is low due to the high calcination temperature in the preparation process of the perovskite oxide, and the valence state of manganese is closely related to the performance of toluene catalytic oxidation, so that how to prepare the perovskite oxide lanthanum manganate with high surface area and adjust the valence state of manganese and use the perovskite oxide lanthanum manganate as a carrier for loading a noble metal catalyst to realize the low-temperature catalysis of toluene is worthy of deep research.
Disclosure of Invention
The invention aims to provide a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium is prepared by the following steps:
(1) adding a silicon template into a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and evaporating, drying, calcining and etching with an alkali solution to obtain a strontium-doped ordered mesoporous lanthanum manganate material;
(2) adding a palladium salt solution into alcohol containing the strontium-doped ordered mesoporous lanthanum manganate material, and performing heating reaction and hydrogen reduction calcination to obtain the composite material containing the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium.
A method for low-temperature thermocatalytic treatment of toluene comprises the following steps:
(1) adding a silicon template into a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and evaporating, drying, calcining and etching with an alkali solution to obtain a strontium-doped ordered mesoporous lanthanum manganate material;
(2) adding a palladium salt solution into alcohol containing a strontium-doped ordered mesoporous lanthanum manganate material, and carrying out heating reaction and reduction to obtain a composite material containing the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium;
(3) the composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium is placed in an environment containing toluene, and is heated at low temperature to complete the removal of toluene by catalytic oxidation.
In the invention, manganese salt is manganese nitrate, lanthanum salt is lanthanum nitrate, strontium salt is strontium nitrate, weak acid is citric acid, alkali is sodium hydroxide, and palladium salt is sodium chloropalladate; in the mixed solution of manganese nitrate, lanthanum nitrate, strontium nitrate and citric acid, the solvent is water; in the sodium hydroxide solution and the sodium chloropalladate solution, the solvents are water; the alcohol is ethanol.
In the invention, the evaporation temperature is room temperature, the time is 10-14 hours, the preferred evaporation temperature is room temperature, and the evaporation time is 12 hours; the drying temperature is 60-100 ℃, the drying time is 4-8 hours, the preferred drying temperature is 80 ℃, and the drying time is 6 hours; the calcination is carried out in the air, and two-stage temperature rise is adopted in the calcination, wherein the temperature rise rate in the first stage is 5 ℃/min, the temperature is 500 ℃, and the time is 5 h; in the second stage, the heating rate is 5 ℃/min, the temperature is 700 ℃, and the time is 8 h; the temperature of the sodium hydroxide solution etching is 70 ℃, and the time is 12 hours.
In the invention, the heating reaction is carried out for 6-10 hours at 50-70 ℃, preferably 8 hours at 60 ℃, and the solvent is removed simultaneously under the thermal evaporation of the solvent; the reduction is hydrogen reduction, the temperature during the reduction treatment is 230-270 ℃, the time is 1.5-2.5 h, preferably, the reduction is calcination in the presence of hydrogen, the calcination temperature is 250 ℃, the time is 2h, and the heating rate is 5 ℃/min.
In the invention, in the step (1), the dosage ratio of the silicon template, the manganese salt, the lanthanum salt, the strontium salt and the weak acid is 1g to 4 mmol (0-3.2) mmol (0.8-4) mmol to 4 mmol, and the prepared strontium-doped ordered mesoporous lanthanum manganate material is La1- xSrxMnO3And x is 0 to 0.8.
In the invention, in the step (2), the palladium salt and the La are mixed1-xSrxMnO3The mass ratio of (1) to (0.01-0.06).
In the invention, silicate ester and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer react in the presence of water and hydrochloric acid, and then are calcined to obtain a silicon template; the reaction is carried out for 24 hours at 38 ℃ and then for 24 hours at 110 ℃; the calcination is carried out for 6 hours at 550 ℃; further, the silicate is tetraethyl orthosilicate.
The method firstly adopts the silicon template as the hard template to prepare the ordered mesoporous lanthanum manganate, obtains a nanotube array structure with higher specific surface area, uniform pore size and good repeatability, can be used as an excellent carrier to load noble metal palladium nanoparticles, and has higher specific surface area which is beneficial to the catalytic reaction. The reduction and calcination treatment is carried out in the atmosphere of hydrogen, the noble metal loaded by the impregnation method is reduced into nano particles loaded into the strontium-doped lanthanum manganate nanotube in the calcination process, so that the nano particles with uniform load and smaller particle size are formed, and the catalytic degradation of toluene can be promoted. After reduction and calcination treatment, the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium is placed in a toluene environment with certain concentration, and is heated and catalyzed by a fixed bed reactor, so that toluene is completely catalyzed and oxidized at low temperature.
The invention further discloses application of the strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium composite material in low-temperature catalytic oxidation of toluene.
The method for treating toluene by low-temperature thermocatalysis disclosed by the invention comprises the steps of putting the strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium composite material into an environment containing toluene, and finishing the treatment of the toluene by using a fixed bed reactor, wherein preferably, the optimal temperature for completely catalyzing and oxidizing toluene gas at low temperature is 150 ℃.
The invention has the advantages that:
the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium has higher specific surface area and uniform pore size, and the doping of strontium is beneficial to the increase of manganese valence state; the noble metal palladium nano particles are loaded on strontium-doped lanthanum manganate, the interaction between the noble metal and the nano particles can improve the performance of catalyzing toluene, the toluene is catalyzed and oxidized at a lower temperature, and the catalyst has a good application prospect.
Drawings
FIG. 1 is a Transmission Electron Micrograph (TEM) of a silicon template;
FIG. 2 is a Scanning Electron Micrograph (SEM) of a silicon template;
FIG. 3 is La0.8rS0.2MnO3Transmission Electron Micrographs (TEMs);
FIG. 4 is La0.8rS0.2MnO3Scanning Electron Micrographs (SEM);
FIG. 5 is a Scanning Electron Micrograph (SEM) of an ordered mesoporous lanthanum manganate (N-LMO) catalyst;
FIG. 6 is a Scanning Electron Micrograph (SEM) of Lanthanum Manganate (LMO) catalyst;
FIG. 7 is 2 wt% Pd @ La0.8rS0.2MnO3Transmission Electron Microscopy (TEM) of the composite;
FIG. 8 is 2 wt% Pd @ La0.8rS0.2MnO3Scanning Electron Micrographs (SEM) of the composite;
FIG. 9 is a graph showing the thermal catalysis effect of strontium-doped ordered mesoporous lanthanum manganate carrier on toluene gas;
FIG. 10 is a graph showing the thermal catalysis effect of a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium on toluene gas;
FIG. 11 is a graph of the catalytic performance of lanthanum manganate LMO' synthesized without the addition of citric acid during the preparation process.
Detailed Description
The preparation method of the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium comprises the following steps:
(1) adding a silicon template into a mixed solution of manganese nitrate, lanthanum nitrate, strontium nitrate and citric acid, and performing evaporation, drying, calcination and sodium hydroxide solution etching to obtain an ordered mesoporous perovskite oxide lanthanum manganate (doped with strontium);
(2) adding the sodium chloropalladate solution into lanthanum manganate (doped with strontium) uniformly dispersed in an ethanol solution, heating and stirring, and performing hydrogen reduction and calcination to obtain the ordered mesoporous perovskite oxide lanthanum manganate-loaded noble metal palladium composite material.
The raw materials involved in the invention are all products conventional in the field, and the specific operation method and the test method are conventional in the field.
Example one ordered mesoporous La0.8rS0.2MnO3The preparation method comprises the following specific steps:
mixing 4g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 130ml of ultrapure water and 20ml of concentrated hydrochloric acid (37 wt%), adding 8.32g of tetraethyl orthosilicate, stirring in a water bath at 38 ℃ for reaction for 24 hours, transferring to a reaction kettle after the reaction is finished, carrying out hydrothermal reaction at 110 ℃ for 24 hours, naturally cooling to room temperature, carrying out suction filtration and washing to be neutral, drying at 80 ℃, and calcining at 10 ℃/min from room temperature to 550 ℃ for 6 hours to obtain the product silicon template.
Adding 3.2 mmol of La (NO)3)3·6H2O，4 mmol Mn(NO3)2，0.8 mmol Sr(NO3)2Dissolving in 5ml of distilled water and 15ml of absolute ethyl alcohol to obtain a uniform solution, then adding 4 mmol of citric acid into the solution, mixing for 1 hour at room temperature, adding 1g of silicon template, and mixing for 12 hours; the solution was then dried in an oven at 80 ℃ for 6 hours, ground thoroughly, calcined in a muffle furnace at 500 ℃ for 5 hours, and then heated to 700 ℃ for 8 hours. The heating rate was 5 deg.C/min throughout the heating process. Finally, the obtained solid product is dispersed in 2M NaOH solution and reflows for 6 h at 70 ℃, so that the ordered mesoporous strontium-doped lanthanum manganate serving as La is obtained0.8Sr0.2MnO3And (3) a carrier.
FIG. 1 is a TEM image of a silicon template, FIG. 2 is an SEM image of a silicon template, and FIG. 3 is La0.8rS0.2MnO3FIG. 4 shows a TEM image of La0.8rS0.2MnO3SEM image of (d). The tubular pore structure can be seen from the figure, and the distribution is uniform.
Modification of La (NO)3)3·6H2O、Sr(NO3)2By the same method, La was obtained0.5Sr0.5MnO3Support, La0.2Sr0.8MnO3And (3) a carrier.
Example two Lanthanum Manganate (LMO) and nano-cast lanthanum manganate (N-LMO) were prepared by the following specific steps:
4 mmol of La (NO)3)3·6H2O，4 mmol Mn(NO3)2And dissolved in 5ml of distilled water and 15ml of absolute ethanol to obtain a uniform solution, then 4 mmol of citric acid is added to the solution and mixed at room temperature for 1 hour, then the solution is dried in an oven at 80 ℃ for 6 hours, after being sufficiently ground, calcined at 500 ℃ for 5 hours in a muffle furnace, and then heated to 700 ℃ for 8 hours.The heating rate was 5 deg.C/min throughout the heating process. Obtaining lanthanum manganate as LaMnO3A carrier (LMO).
4 mmol of La (NO)3)3·6H2O，4 mmol Mn(NO3)2Dissolving the mixture in 5ml of distilled water and 15ml of absolute ethyl alcohol to obtain a uniform solution, then adding 4 mmol of citric acid into the solution, mixing for 1 hour at room temperature, adding 1g of silicon template, and mixing for 12 hours; the solution was then dried in an oven at 80 ℃ for 6 hours, ground thoroughly, calcined in a muffle furnace at 500 ℃ for 5 hours, and then heated to 700 ℃ for 8 hours. The heating rate was 5 deg.C/min throughout the heating process. Finally, the obtained solid product is dispersed in 2M NaOH solution and refluxed for 6 h at 70 ℃, so that ordered mesoporous lanthanum manganate serving as LaMnO is obtained3Carrier (N-LMO).
FIG. 5 is an SEM image of an ordered mesoporous lanthanum manganate (N-LMO) catalyst, and FIG. 6 is an SEM image of a Lanthanum Manganate (LMO) catalyst.
The preparation method of the composite material of the strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium comprises the following specific steps:
a certain amount of sodium chloropalladate solution (1 wt%, 2 wt%, 4 wt%, 6 wt%) is added with La0.8Sr0.2MnO3Base carrier) was added to 120mg of La dispersed in 15mL of ethanol0.8Sr0.2MnO3Stirring with conventional magnetic force at 60 deg.C for 8 hr to obtain black powder, and adding 10 vol% H2/N2Calcining in the atmosphere, wherein the calcining temperature is 250 ℃, the calcining time is 2h, and the heating rate is 10 ℃/min, so as to obtain the strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material, wherein the palladium-supported mass accounts for La0.8Sr0.2MnO32% of the sample is noted as 2 wt% Pd La0.8rS0.2MnO3。
FIG. 7 is a TEM image of the composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, and FIG. 8 is an SEM image of the composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium. It can be seen from the figure that the morphology of the perovskite oxide is well controlled, and the perovskite oxide is not obviously changed after being loaded with noble metal.
In the fourth embodiment, lanthanum manganate is synthesized without adding citric acid, and the specific steps are as follows:
4 mmol of La (NO)3)3·6H2O，4 mmol Mn(NO3)2And dissolved in 5ml of distilled water and 15ml of absolute ethanol to obtain a homogeneous solution, and then the solution is dried in an oven at 80 ℃ for 6 hours, ground sufficiently, calcined at 500 ℃ for 5 hours in a muffle furnace, and then heated to 700 ℃ for 8 hours. The heating rate was 5 deg.C/min throughout the heating process. The lanthanum manganate nanoparticles are obtained and are marked as LMO'.
Example thermal catalysis conditions of the composite material of the strontium pentadoped ordered mesoporous lanthanum manganate supported noble metal palladium on toluene gas are as follows: the toluene concentration was 50 ppm, the amount of the catalyst was 50 mg, the catalyst was fixed to a fixed bed reactor through a U-shaped tube, and the catalytic effect of the composite material on toluene gas under heating was analyzed by gas chromatography.
FIG. 9 is a graph showing the thermal catalysis effect of strontium-doped ordered mesoporous lanthanum manganate carrier on toluene gas. FIG. 10 is a graph showing the thermal catalysis effect of the composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium on toluene gas. FIG. 11 is a graph of the catalytic performance of lanthanum manganate LMO' synthesized without the addition of citric acid during the preparation process. As can be seen from FIGS. 9 and 10, the present invention is applicable to the conversion of toluene at lower temperatures. The toluene pollution in the air mainly comes from building materials, interior decoration materials, living and office supplies, outdoor industrial waste gas, automobile exhaust, photochemical smog and the like, the specific toluene catalytic effect is analyzed through gas chromatography, and the calculation method of the toluene conversion rate is as the equation (1):
C0and C are the initial and test concentrations of toluene in the experiment (every 15 minutes).
FIG. 9 is a comparison of catalytic effects of strontium-doped ordered mesoporous lanthanum manganate carrier on toluene gas, showing that the introduction of strontium significantly reduces the catalytic reaction temperature; FIG. 10 is a graph showing the thermal catalytic effect of the composite material of strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium on toluene gas, and the noble metal loading further reduces the catalytic temperature, which shows that the strong interaction between the noble metal and the perovskite oxide can promote the degradation of toluene, and the complete conversion of toluene can be realized at 150 ℃. Comparing figure 9 with figure 11, it can be seen that the addition of citric acid favours the catalytic oxidation of toluene.
Through the analysis, the technical scheme of the invention is proved to be capable of successfully controlling the shape of lanthanum manganate, strontium in different proportions is introduced into the lanthanum manganate to adjust the valence state of manganese, the strontium-doped lanthanum manganate with higher specific surface area can be used as a good carrier to uniformly load noble metal palladium nanoparticles, the stability and efficiency of the catalyst are improved under the interaction of the carrier and noble metal, the catalytic oxidation of toluene at lower temperature is realized, and the catalyst has good application prospect in the practical application process.
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| CN114628705A (en) * | 2022-03-21 | 2022-06-14 | 北京单原子催化科技有限公司 | Catalyst containing lanthanum strontium metal oxide with strontium-deficient surface, preparation and application |
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