CN112337461B - Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene - Google Patents
Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene Download PDFInfo
- Publication number
- CN112337461B CN112337461B CN202011160066.9A CN202011160066A CN112337461B CN 112337461 B CN112337461 B CN 112337461B CN 202011160066 A CN202011160066 A CN 202011160066A CN 112337461 B CN112337461 B CN 112337461B
- Authority
- CN
- China
- Prior art keywords
- strontium
- toluene
- ordered mesoporous
- noble metal
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 135
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 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 title claims abstract description 63
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 43
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 title abstract description 19
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 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
- 238000005530 etching Methods 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
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000002603 lanthanum Chemical class 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 150000002940 palladium Chemical class 0.000 claims description 7
- 159000000008 strontium salts Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 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
- 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 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 11
- 239000011572 manganese Substances 0.000 abstract description 11
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002071 nanotube Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000008139 complexing agent Substances 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 abstract 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 1
- 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
- 239000003054 catalyst Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002578 La0.2Sr0.8MnO3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a strontium-doped ordered mesoporous lanthanum manganate supported noble metal palladium composite material, a preparation method thereof and application thereof in catalytic oxidation of toluene, and La (NO) 3 ) 3 ·6H 2 O,Mn(NO 3 ) 2 ,Sr(NO 3 ) 2 As lanthanum source, manganese source and strontium source, silicon template molecular sieve as hard template, citric acid as complexing agent, and evaporating, drying, calcining and sodium hydroxide solution etching to obtain La 1‑ x Sr x MnO 3 A nanotube material; taking La 1‑x Sr x MnO 3 Adding sodium chloropalladate metal precursor as carrier, stirring, solvent thermal evaporating and hydrogen reducing calcining to obtain La with supported palladium 1‑x Sr x MnO 3 Nanotube composites. Pd@La of the invention 1‑x Sr x MnO 3 The introduction of strontium in the composite material increases the content of tetravalent manganese so as to promote the catalytic oxidation of toluene, realize the efficient catalytic oxidation of toluene at a lower temperature, and have good application prospects for degrading the polluted gas toluene discharged in industrial production and life.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium composite material, a preparation method thereof and application thereof in catalytic oxidation of toluene.
Background
Volatile Organic Compounds (VOCs) are important precursors that cause atmospheric complex pollution such as urban haze and photochemical pollution, have a great influence on human health and ecological environment, and have attracted extensive attention from government and public. The current treatment method for VOCs mainly comprises the following steps: adsorption, absorption, membrane separation, plasma, photocatalysis, catalytic oxidation, and the like. Among them, the catalytic oxidation method is widely used because it has low operating temperature, high efficiency and low energy consumption, and the key problem of the method is to develop and develop a catalyst with low temperature, high activity, good thermal stability and low cost. Noble metal catalysts have been widely studied for their excellent catalytic performance, but since noble metals are easily agglomerated and deactivated during application, a support having a large surface area and being stable is required to support the noble metal materials.
The perovskite oxide has rich reserves and good oxidation-reduction capability, the surface area of the perovskite oxide is lower due to high calcination temperature in the preparation process of the perovskite oxide, and the valence state of manganese is closely related to the performance of catalytic oxidation of toluene, so that the low-temperature catalysis of toluene is worth intensive research on how to prepare perovskite oxide lanthanum manganate with high surface area, adjust the valence state of manganese and take the perovskite oxide as a carrier for loading a noble metal catalyst.
Disclosure of Invention
The invention aims to provide a strontium-doped ordered mesoporous lanthanum manganate composite material loaded with noble metal palladium and a preparation method thereof, wherein the ordered mesoporous lanthanum manganate is prepared by adopting a nano casting method and doped with strontium in different proportions, and the noble metal palladium in different proportions is loaded on the surface of the lanthanum manganate by utilizing a hydrogen reduction method so as to realize efficient catalytic oxidation of toluene.
In order to achieve the above purpose, the invention adopts the following specific technical scheme:
the preparation method of the strontium-doped ordered mesoporous lanthanum manganate supported noble metal palladium composite material comprises the following steps:
(1) Adding a silicon template into a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and performing evaporation, drying, calcination and alkali solution etching to obtain a strontium-doped ordered mesoporous lanthanum manganate material;
(2) And adding palladium salt solution into alcohol containing the strontium-doped ordered mesoporous lanthanum manganate material, and obtaining the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium composite material through heating reaction and hydrogen reduction calcination.
A method for low temperature catalytic treatment of toluene comprising the steps of:
(1) Adding a silicon template into a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and performing evaporation, drying, calcination and alkali solution etching to obtain a strontium-doped ordered mesoporous lanthanum manganate material;
(2) Adding palladium salt solution into alcohol containing strontium-doped ordered mesoporous lanthanum manganate material, and obtaining a composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium through heating reaction and reduction;
(3) Putting the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium composite material into an environment containing toluene, and heating at a low temperature to complete catalytic oxidation to remove the toluene.
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 solvent is water; the alcohol is ethanol.
In the invention, the evaporating temperature is room temperature, the evaporating time is 10-14 hours, the preferable evaporating temperature is room temperature, and the evaporating time is 12 hours; the drying temperature is 60-100 ℃, the time is 4-8 hours, the preferable drying temperature is 80 ℃, and the drying time is 6 hours; calcining is carried out in air, wherein the calcining adopts two-stage heating, the heating rate in the first stage is 5 ℃/min, the temperature is 500 ℃, and the time is 5h; the temperature rising rate in the second stage is 5 ℃/min, the temperature is 700 ℃ and the time is 8h; the temperature of the sodium hydroxide solution etching was 70℃for 12 hours.
In the invention, the heating reaction is carried out for 6-10 hours at 50-70 ℃, preferably for 8 hours at 60 ℃, and the solvent is removed simultaneously under the condition of solvent thermal evaporation; reducing to hydrogen, wherein the temperature of the reduction treatment is 230-270 ℃, the time is 1.5-2.5 h, preferably, the reduction is calcining in the presence of hydrogen, the calcining 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 1 g:4 mmol (0-3.2 mmol) (0.8-4 mmol) and 4 mmol, and the prepared strontium-doped ordered mesoporous lanthanum manganate material is La 1- x Sr x MnO 3 X is 0 to 0.8.
In the invention, the palladium salt and La in the step (2) 1-x Sr x MnO 3 The mass ratio of (1) is (0.01-0.06).
In the invention, silicate reacts with polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in the presence of water and hydrochloric acid, and then the silicate is calcined to obtain a silicon template; the reaction is carried out for 24 hours at 38 ℃ and then for 24 hours at 110 ℃; calcining at 550 ℃ for 6 hours; further, the silicate is tetraethyl orthosilicate.
According to the invention, the ordered mesoporous lanthanum manganate is prepared by adopting a method of taking a silicon template as a hard template, so that the nanotube array structure with higher specific surface area, uniform pore size and good repeatability is obtained, the nanotube array structure can be used as an excellent carrier to load noble metal palladium nano particles, and the higher specific surface area is favorable for carrying out catalytic reaction. The reduction calcination treatment is carried out in a hydrogen atmosphere, noble metal loaded by an impregnation method is reduced into nano particles loaded into the strontium-doped lanthanum manganate nanotube in the calcination, so that nano particles with uniform loading and smaller particle size are formed, and the catalytic degradation of toluene can be promoted. After reduction and calcination treatment, the quantitative strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium composite material is placed in a toluene environment with a certain concentration, and is heated and catalyzed by a fixed bed reactor, so that toluene is completely catalyzed and oxidized at a 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.
In the method for low-temperature catalytic treatment of toluene, the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium is placed in an environment containing toluene, and a fixed bed reactor is utilized to finish the treatment of toluene, and preferably, the optimal temperature of low-temperature complete catalytic oxidation toluene gas 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 the valence state of manganese; the noble metal palladium nano particles are loaded on the strontium-doped lanthanum manganate, and the interaction between the noble metal and the nano particles can improve the performance of catalyzing toluene, so that the toluene is catalytically oxidized at a lower temperature, and the method has a good application prospect.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) of a silicon template;
FIG. 2 is a Scanning Electron Microscope (SEM) of a silicon template;
FIG. 3 is La 0.8r S 0.2 MnO 3 A Transmission Electron Microscope (TEM);
FIG. 4 is La 0.8r S 0.2 MnO 3 Scanning Electron Microscope (SEM);
FIG. 5 is a Scanning Electron Microscope (SEM) of an ordered mesoporous lanthanum manganate (N-LMO) catalyst;
FIG. 6 is a Scanning Electron Microscope (SEM) of a Lanthanum Manganate (LMO) catalyst;
FIG. 7 is a graph of 2wt% Pd@La 0.8r S 0.2 MnO 3 Transmission electron microscope image of composite material（TEM）；
FIG. 8 is a graph of 2wt% Pd@La 0.8r S 0.2 MnO 3 Scanning Electron Microscopy (SEM) of the composite;
FIG. 9 is a graph of the thermal catalytic effect of a strontium doped ordered mesoporous lanthanum manganate support on toluene gas;
FIG. 10 is a graph of the thermal catalytic 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 showing the catalytic performance of lanthanum manganate LMO' synthesized without citric acid added during the preparation process.
Detailed Description
The preparation method of the strontium-doped ordered mesoporous lanthanum manganate supported noble metal palladium composite material 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 steps to obtain ordered mesoporous perovskite oxide lanthanum manganate (strontium doped);
(2) Adding the sodium chloropalladate solution into lanthanum manganate (strontium doped) which is uniformly dispersed in ethanol solution, and carrying out hydrogen reduction calcination by heating and stirring to obtain the ordered mesoporous perovskite oxide lanthanum manganate loaded noble metal palladium composite material.
The raw materials involved in the invention are all conventional products in the field, and the specific operation method and the testing method are conventional methods in the field.
Example one ordered mesoporous La 0.8r S 0.2 MnO 3 The preparation method comprises the following specific steps:
4g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 130ml of ultrapure water and 20ml of concentrated hydrochloric acid (37 wt%) are mixed, then 8.32g of tetraethyl orthosilicate is added, the mixture is stirred and reacted for 24 hours in a water bath at 38 ℃, after the reaction, the mixture is transferred into a reaction kettle to be subjected to hydrothermal reaction at 110 ℃ for 24 hours, the mixture is naturally cooled to room temperature, filtered by suction and washed to be neutral, dried at 80 ℃, and calcined at 10 ℃/min from room temperature to 550 ℃ for 6 hours to obtain a product silicon template.
3.2 mmol of La (NO 3 ) 3 ·6H 2 O，4 mmol Mn(NO 3 ) 2 ，0.8 mmol Sr(NO 3 ) 2 Dissolving in 5ml distilled water and 15ml absolute ethanol to obtain a uniform solution, adding 4 mmol citric acid into the solution, mixing for 1 hour at room temperature, adding 1g silicon template, and mixing for 12 hours; the solution was then dried in an oven at 80 ℃ for 6 hours, after sufficient grinding, calcined in a muffle furnace at 500 ℃ for 5h, and then heated to 700 ℃ for 8 h. The heating rate was 5 deg.c/min throughout the heating process. Finally, dispersing the obtained solid product in 2M NaOH solution, refluxing for 6 h at 70 ℃ to obtain ordered mesoporous Kong Cansi lanthanum manganate serving as La 0.8 Sr 0.2 MnO 3 A carrier.
FIG. 1 is a TEM image of a silicon template, FIG. 2 is an SEM image of a silicon template, FIG. 3 is La 0.8r S 0.2 MnO 3 Is a TEM image of La of FIG. 4 0.8r S 0.2 MnO 3 SEM images of (a). The tubular duct structure can be seen from the figure, and the distribution is more uniform.
Modification of La (NO) 3 ) 3 ·6H 2 O、Sr(NO 3 ) 2 In the same manner, la was obtained 0.5 Sr 0.5 MnO 3 Carrier, la 0.2 Sr 0.8 MnO 3 A carrier.
Example two Lanthanum Manganate (LMO) and nano-cast lanthanum manganate (N-LMO) were prepared as follows:
4 mmol of La (NO) 3 ) 3 ·6H 2 O，4 mmol Mn(NO 3 ) 2 Dissolving in 5ml distilled water and 15ml absolute ethanol to obtain a uniform solution, adding 4 mmol citric acid into the solution, mixing for 1 hour at room temperature, drying the solution in an oven at 80 ℃ for 6 hours, calcining for 5h at 500 ℃ in a muffle furnace after fully grinding, and heating to 700 ℃ to calcine for 8 h. The heating rate was 5 deg.c/min throughout the heating process. Lanthanum manganate is obtained as LaMnO 3 A carrier (LMO).
4 mmol of La (NO) 3 ) 3 ·6H 2 O，4 mmol Mn(NO 3 ) 2 Dissolving in waterDissolving in 5ml distilled water and 15ml absolute ethanol to obtain a uniform solution, adding 4 mmol citric acid into the solution, mixing for 1 hour at room temperature, adding 1g silicon template, and mixing for 12 hours; the solution was then dried in an oven at 80 ℃ for 6 hours, after sufficient grinding, calcined in a muffle furnace at 500 ℃ for 5h, and then heated to 700 ℃ for 8 h. The heating rate was 5 deg.c/min throughout the heating process. Finally, dispersing the obtained solid product in 2M NaOH solution, refluxing for 6 h at 70 ℃ to obtain ordered mesoporous lanthanum manganate serving as LaMnO 3 Vector (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 three-strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium comprises the following specific steps:
an amount of sodium chloropalladate solution (1 wt%, 2wt%, 4wt%, 6wt%, la 0.8 Sr 0.2 MnO 3 Carriers base) was added to 120mg La dispersed in 15mL ethanol 0.8 Sr 0.2 MnO 3 In the carrier, the mixture was magnetically stirred at 60℃for 8 hours to give a black powder, and the black powder was stirred at 10vol% H 2 /N 2 Calcining in atmosphere at 250 ℃ for 2h at a heating rate of 10 ℃/min to obtain the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium, wherein the palladium loading mass accounts for La 0.8 Sr 0.2 MnO 3 2% of the sample was recorded as 2wt% Pd La 0.8r S 0.2 MnO 3 。
Fig. 7 is a TEM image of a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, and fig. 8 is an SEM image of a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium. From the graph, 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 under the condition of no citric acid, and the specific steps are as follows:
4 mmol of La (NO) 3 ) 3 ·6H 2 O，4 mmol Mn(NO 3 ) 2 Dissolving in 5ml distilled water and 15ml absolute ethanol to obtain a uniform solution, then drying the solution in an oven at 80 ℃ for 6 hours, calcining 5h in a muffle furnace at 500 ℃ after fully grinding, and then heating to 700 ℃ to calcine 8 h. The heating rate was 5 deg.c/min throughout the heating process. Lanthanum manganate nanoparticles were obtained, denoted LMO'.
The thermal catalysis conditions of the composite material of the five-strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium on toluene gas are as follows: toluene concentration was 50 ppm and the amount of catalyst was 50 mg, and the catalyst was fixed on a fixed bed reactor through a U-tube, and the catalytic effect of the composite material on toluene gas under heating was analyzed by gas chromatography.
Fig. 9 is a graph of the thermal catalytic effect of strontium doped ordered mesoporous lanthanum manganate carrier on toluene gas. FIG. 10 is a graph of the thermal catalytic 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 showing the catalytic performance of lanthanum manganate LMO' synthesized without citric acid added during the preparation process. As can be seen from fig. 9 and 10, the present invention can be applied to toluene conversion at lower temperatures. The toluene pollution in the air mainly comes from building materials, interior decoration materials and articles for life and offices, outdoor industrial waste gas, automobile exhaust, photochemical smog and the like, the specific toluene catalytic effect is analyzed by gas chromatography, and the calculation method of the toluene conversion rate is as shown in equation (1):
C 0 and C is the initial and test concentrations of toluene in the experiment (once every 15 minutes).
FIG. 9 is a comparison of the catalytic effect of strontium doped ordered mesoporous lanthanum manganate carrier on toluene gas, and it can be seen that the introduction of strontium significantly reduces the catalytic reaction temperature; fig. 10 is a graph of the thermal catalytic effect of a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium on toluene gas, wherein the noble metal loading further reduces the catalytic temperature, which illustrates that the strong interaction between the noble metal and perovskite oxide can promote the degradation of toluene, and the complete conversion of toluene can be realized at 150 ℃. Comparing fig. 9 with fig. 11, it can be seen that the addition of citric acid favors the catalytic oxidation of toluene.
Through the analysis, the technical scheme of the invention is shown that the morphology of lanthanum manganate can be successfully controlled, the valence state of manganese can be adjusted by introducing strontium with different proportions into lanthanum manganate, the strontium-doped lanthanum manganate with higher specific surface area can be used as a good carrier to uniformly load noble metal palladium nano particles, the stability and the efficiency of the catalyst are improved under the interaction of the carrier and noble metal, the toluene is catalytically oxidized at a lower temperature, and the catalyst has good application prospect in the practical application process.
Claims (5)
1. The preparation method of the strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium composite material is characterized by comprising the following steps of:
(1) Reacting silicate with polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in the presence of water and hydrochloric acid, and calcining to obtain a silicon template; adding a silicon template into a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and performing evaporation, drying, calcination and alkali solution etching to obtain a strontium-doped ordered mesoporous lanthanum manganate material;
(2) Adding palladium salt solution into alcohol containing strontium-doped ordered mesoporous lanthanum manganate material, and obtaining the composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded noble metal palladium through heating reaction and hydrogen reduction calcination;
the manganese salt is manganese nitrate, the lanthanum salt is lanthanum nitrate, the strontium salt is strontium nitrate, the weak acid is citric acid, the alkali is sodium hydroxide, and the palladium salt is sodium chloropalladate; the dosage ratio of the silicon template, the manganese salt, the lanthanum salt, the strontium salt and the weak acid is 1 g:4 mmol, 3.2 mmol and 0.8mmol and 4 mmol; palladium salt and La 1-x Sr x MnO 3 The mass ratio of (2) is 0.02:1;
the evaporating temperature is room temperature and the evaporating time is 10-14 hours; the drying temperature is 60-100 ℃ and the drying time is 4-8 hours; the calcination is carried out in air, and the calcination adopts two-stage heating.
2. The composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium according to claim 1, wherein the heating reaction is carried out for 6-10 hours at 50-70 ℃.
3. The composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium according to claim 1, wherein the reduction is carried out by hydrogen, the temperature during the reduction is 230-270 ℃ and the time is 1.5-2.5 h.
4. The composite material of the strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium as claimed in claim 1, which is characterized by application in low-temperature catalytic oxidation of toluene; the low-temperature heating temperature is 140-160 ℃.
5. A method for low-temperature catalytic treatment of toluene is characterized in that a composite material of strontium-doped ordered mesoporous lanthanum manganate loaded with noble metal palladium according to claim 1 is placed in an environment containing toluene, heated at low temperature and catalytic oxidation is completed to remove toluene; the low-temperature heating temperature is 140-160 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011160066.9A CN112337461B (en) | 2020-10-26 | 2020-10-26 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
| PCT/CN2021/141006 WO2022089669A1 (en) | 2020-10-26 | 2021-12-23 | Composite material of strontium-doped ordered mesoporous lanthanum manganite loaded with precious metal palladium, and preparation method therefor and use thereof in catalytic oxidation of toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011160066.9A CN112337461B (en) | 2020-10-26 | 2020-10-26 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112337461A CN112337461A (en) | 2021-02-09 |
| CN112337461B true CN112337461B (en) | 2023-11-03 |
Family
ID=74359032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011160066.9A Active CN112337461B (en) | 2020-10-26 | 2020-10-26 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112337461B (en) |
| WO (1) | WO2022089669A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337461B (en) * | 2020-10-26 | 2023-11-03 | 苏州大学 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
| CN114628705B (en) * | 2022-03-21 | 2023-06-02 | 北京单原子催化科技有限公司 | Catalyst containing lanthanum strontium metal oxide with surface deficient strontium, preparation and application |
| CN114669291A (en) * | 2022-05-06 | 2022-06-28 | 南京工业大学 | Catalyst particle with inverse protein structure for catalytic oxidation of methane and preparation method thereof |
| CN115569647A (en) * | 2022-09-07 | 2023-01-06 | 浙江大学杭州国际科创中心 | Composite oxide catalyst and preparation method and application thereof |
| CN115582123B (en) * | 2022-11-01 | 2023-10-10 | 大连海事大学 | Porous metal oxide catalyst, preparation method thereof and application thereof in plasma catalytic system |
| CN115957759B (en) * | 2022-12-12 | 2023-09-08 | 河南农业大学 | Manganese-based synergistic monolithic catalyst and preparation method and application thereof |
| CN116196921B (en) * | 2022-12-20 | 2024-06-04 | 北京工业大学 | Three-dimensional ordered macroporous lanthanum manganate supported palladium monoatomic catalyst for purifying tail gas of natural gas vehicle |
| CN116726911B (en) * | 2023-06-19 | 2024-06-11 | 金华职业技术学院 | Mn (Mn)5O8Ozone normal temperature decomposition catalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389792A (en) * | 2011-09-29 | 2012-03-28 | 北京工业大学 | Three-dimensional ordered macroporous LaMnO3 supported high-dispensability MnOx catalyst and preparation method and use thereof |
| CN103962127A (en) * | 2014-05-16 | 2014-08-06 | 华东理工大学 | Method and catalyst for performing low-temperature catalytic combustion to eliminate chlorination aromatic hydrocarbon |
| CN106166491A (en) * | 2016-07-22 | 2016-11-30 | 武汉理工大学 | A kind of mesoporous La0.8sr0.2coO3load nano Ce O2catalyst and its preparation method and application |
| CN107456964A (en) * | 2017-08-23 | 2017-12-12 | 清华大学 | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation |
| CN111185182A (en) * | 2020-03-06 | 2020-05-22 | 清华大学 | Perovskite catalyst and preparation method and application thereof |
| CN111229238A (en) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | Ordered porous perovskite catalyst for synergistically catalyzing and oxidizing NO and toluene and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431693C (en) * | 2006-11-10 | 2008-11-12 | 北京工业大学 | Process for preparing catalyst contg. La(1-x)SrxMO3 used for removing volatile organic matter |
| WO2014038294A1 (en) * | 2012-09-10 | 2014-03-13 | 日産自動車株式会社 | Exhaust gas purification catalyst, exhaust gas purification monolith catalyst, and method for producing exhaust gas purification catalyst |
| CN104607201B (en) * | 2014-12-18 | 2017-01-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof |
| CN105289602A (en) * | 2015-12-01 | 2016-02-03 | 福建紫荆环境工程技术有限公司 | Ceria-zirconia composite oxide-loaded perovskite type catalyst with sulfur resistance and preparation method of catalyst |
| CN106410226B (en) * | 2016-12-08 | 2019-03-05 | 深圳大学 | Graphene doping vario-property nano-perovskite type La1-xSrxMnO3 composite material and preparation method and application |
| CN106881096A (en) * | 2017-03-31 | 2017-06-23 | 武汉理工大学 | Mesoporous LaFeO3The preparation method of perovskite type composite oxide catalyst material |
| CN112337461B (en) * | 2020-10-26 | 2023-11-03 | 苏州大学 | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene |
-
2020
- 2020-10-26 CN CN202011160066.9A patent/CN112337461B/en active Active
-
2021
- 2021-12-23 WO PCT/CN2021/141006 patent/WO2022089669A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389792A (en) * | 2011-09-29 | 2012-03-28 | 北京工业大学 | Three-dimensional ordered macroporous LaMnO3 supported high-dispensability MnOx catalyst and preparation method and use thereof |
| CN103962127A (en) * | 2014-05-16 | 2014-08-06 | 华东理工大学 | Method and catalyst for performing low-temperature catalytic combustion to eliminate chlorination aromatic hydrocarbon |
| CN106166491A (en) * | 2016-07-22 | 2016-11-30 | 武汉理工大学 | A kind of mesoporous La0.8sr0.2coO3load nano Ce O2catalyst and its preparation method and application |
| CN107456964A (en) * | 2017-08-23 | 2017-12-12 | 清华大学 | For the extra specific surface area perovskite type composite oxide catalyst of hydrocarbon low-temperature oxidation and its preparation |
| CN111229238A (en) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | Ordered porous perovskite catalyst for synergistically catalyzing and oxidizing NO and toluene and preparation method and application thereof |
| CN111185182A (en) * | 2020-03-06 | 2020-05-22 | 清华大学 | Perovskite catalyst and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "Ag/La0.6Sr0.4MnO3基催化剂上CH3OH和CO的完全氧化";王伟等;《燃料化学学报》;20000229;第28卷(第1期);第8-15页 * |
| "Au改性La0.8Sr0.2MnO3催化剂的催化燃烧性能";卢晗锋等;《化工学报》;20080430;第59卷(第4期);第892-897页 * |
| "High Performance Au−Pd Supported on 3D Hybrid StrontiumSubstituted Lanthanum Manganite Perovskite Catalyst for Methane Combustion";Yuan Wang et al.;《ACS Catalysis》;20160906;第6卷;摘要、图6、表1-2和Supporting Information * |
| "Strontium-Doped Lanthanum Cobaltite and Manganite: Highly Active Catalysts for Toluene Complete Oxidation";Jiguang Deng et al.;《Ind. Eng. Chem. Res.》;20081008;第47卷;第8175-8183页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112337461A (en) | 2021-02-09 |
| WO2022089669A1 (en) | 2022-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112337461B (en) | Composite material of strontium doped ordered mesoporous lanthanum manganate loaded with noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene | |
| CN107824210B (en) | Titanium dioxide composite photocatalyst coated by nitrogen-doped mesoporous carbon and preparation method and application thereof | |
| CN109772465B (en) | Preparation method of water-soluble carbon dot modified perovskite type catalytic material | |
| CN110681382B (en) | MOF-cobalt-based metal oxide catalyst for catalytic oxidation of toluene and preparation method thereof | |
| CN110694619B (en) | Platinum and ruthenium bimetal loaded zirconium oxide nanotube composite material, preparation method thereof and application thereof in low-temperature thermal catalytic treatment of toluene | |
| CN113976155A (en) | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation | |
| CN109433190B (en) | Mesoporous zirconia nanotube composite material loaded with platinum nanoparticles, preparation method thereof and application thereof in continuous treatment of organic waste gas | |
| CN108380203B (en) | Mesoporous wall hollow core-shell spherical LaMnO3Perovskite catalyst and preparation method thereof | |
| CN110314685B (en) | Preparation method of core-shell structure catalyst for low-temperature catalytic oxidation of toluene | |
| CN113680343B (en) | Three-dimensional cubic CeO 2 /Mn 2 O 3 Preparation method and application of composite photo-thermal catalyst | |
| Ru et al. | Regulating the surface local environment of MnO2 materials via metal-support interaction in Pt/MnO2 hetero-catalysts for boosting methanol oxidation | |
| CN110935309B (en) | Two-stage low-concentration VOC catalytic degradation method | |
| CN110302819B (en) | MOFs-derived bimetallic magnetic nanoporous carbon ozone catalyst and application thereof | |
| CN114849698B (en) | Mesoporous Na-alpha-MnO 2 Catalyst, preparation method and application thereof | |
| CN114433073B (en) | Manganese-based catalyst and preparation method and application thereof | |
| CN114797847B (en) | Metal doped mesoporous carbon-based catalyst and preparation method and application thereof | |
| CN112452335B (en) | Ternary NiO nano sheet @ bimetal CeCuOxMicro-sheet core-shell structure composite material and preparation and application thereof | |
| CN114632516B (en) | Nanosheet catalyst for catalytic oxidation of VOC (volatile organic compounds) and preparation and application methods thereof | |
| CN113522273B (en) | Preparation method of oxygen vacancy-rich tungsten trioxide and application of oxygen vacancy-rich tungsten trioxide in photocatalytic reaction | |
| CN111790378B (en) | Manganese dioxide loaded PtPd bimetallic nanosphere and preparation method and application thereof | |
| CN113926480A (en) | Preparation method of metal alloy modified layered perovskite structure photocatalyst | |
| CN114308061A (en) | NiAu bimetallic alloy nano catalyst and synthesis and application thereof | |
| CN115350708B (en) | Composite catalyst, preparation method and application thereof | |
| CN114797932B (en) | Bimetallic 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof | |
| CN112452129B (en) | Ternary NiO nanosheet @ bimetal CeCuOxMethod for low-temperature heat treatment of toluene by using microchip core-shell structure composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |