CN111921522A - Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof - Google Patents
Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof Download PDFInfo
- Publication number
- CN111921522A CN111921522A CN201910392081.7A CN201910392081A CN111921522A CN 111921522 A CN111921522 A CN 111921522A CN 201910392081 A CN201910392081 A CN 201910392081A CN 111921522 A CN111921522 A CN 111921522A
- Authority
- CN
- China
- Prior art keywords
- antimony
- doped tin
- tin oxide
- manganese oxide
- manganese
- 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.)
- Pending
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- LINIVNYLYFRMRI-UHFFFAOYSA-N [O-2].[Mn+2].[Sn+2]=O.[O-2] Chemical compound [O-2].[Mn+2].[Sn+2]=O.[O-2] LINIVNYLYFRMRI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title claims description 47
- 230000003647 oxidation Effects 0.000 title claims description 12
- 238000007254 oxidation reaction Methods 0.000 title claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 160
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 73
- 229910001887 tin oxide Inorganic materials 0.000 claims description 72
- 239000002105 nanoparticle Substances 0.000 claims description 37
- 239000002070 nanowire Substances 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 239000002135 nanosheet Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical group [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920002866 paraformaldehyde Polymers 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 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
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
Images
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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 relates to an antimony-doped tin oxide-manganese oxide composite catalyst for catalyzing and oxidizing formaldehyde at room temperature and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to an antimony-doped tin oxide-manganese oxide composite catalyst for catalyzing and oxidizing formaldehyde at room temperature and a preparation method thereof.
Background
With the rapid development of economy, the human industrialization process is accelerated continuously, the living standard of people is improved continuously, but at the same time, the people rely on the environment for survival to faceThe pressure is also increasing. In recent years, indoor air pollution, which is followed by soot pollution and photochemical pollution, becomes a main environmental pollution problem which is harmful to human health, and is receiving more and more extensive attention. Among the most important pollutants are Volatile Organic Compounds (VOCs), which generally include alcohols, ketones, aldehydes, and various olefins, aromatics, naphthenes, etc., wherein formaldehyde gas is an Organic gaseous pollutant that is frequently exposed to indoor environments. The formaldehyde gas can be released from various building materials, decoration materials, furniture and the like used in indoor and decoration, the release period can be as long as 15 years at most, the health of people is harmed for a long time, and researches show that 65% of human body diseases are related to indoor pollution. According to the regulation of indoor air quality standard (GB/T18883-2002) issued by China, the sanitary standard (maximum allowable concentration) of formaldehyde in indoor air is 0.08mg/m3How to remove formaldehyde efficiently in a room temperature environment becomes a research hotspot of the present society.
Supported noble metal catalysts, which are attracting much attention because of their excellent low-temperature oxidation activity, mainly comprise noble metals such as Pt, Au, Pd and Ag as active components and are supported on various metal oxides (TiO)2、Al2O3、MnO2、ZrO2And Fe2O3Etc.) and mixtures thereof, thereby avoiding the problems of susceptibility to oxidation and sintering of the individual noble metals. However, the precious metal resources are scarce and expensive, and a small amount of sulfur and nitrogen oxides in the air easily deactivate the toxicity thereof in the using process, so that the defects greatly limit the wide application of the precious metal resources in practice. Therefore, the development of non-noble metal catalysts that are economical, practical and capable of efficiently catalytically oxidizing formaldehyde has become a focus of research. In recent years, a transition metal oxide catalyst having a good activity (complete oxidation temperature T)100At 140 ℃ or lower) mainly comprises MnOx、Co3O4And Cr2O3Etc. in the case of single metal oxides not having good catalytic properties, other metal elements such as Ce, Sn, Cu, Zr, etc. may be doped to MnOxAnd Co3O4Preparation of composite metal oxygenAnd (4) melting the mixture. Among them, the manganese oxide catalyst has been widely paid attention and studied due to its characteristics of low cost, easy availability, high catalytic activity at high temperature, strong resistance to sulfur and toxicity, etc., and is considered as one of the main choices for replacing noble metal catalysts. However, the manganese oxide catalysts reported at present still have the problems of low Catalytic efficiency at room temperature and excessive complete degradation temperature, Zhang et al (Catalytic oxidation of formaldehyde over catalyst with a differential crystal structure)&Technology,2015,5(4):2305-2313) found different morphologies of α -MnO2、β-MnO2And gamma-MnO2The temperatures at which the catalyst completely converts formaldehyde under the same conditions were 125 ℃, 200 ℃ and 150 ℃, respectively. In recent years, nanometer antimony-doped tin oxide (ATO) has been applied to solar cells, sensors, electrodes and other aspects as an important conductive oxide and strong near infrared absorption material due to the advantages of low cost, low resistivity, good thermal conductivity, good electrical conductivity, good chemical stability and the like, but the application of the nanometer antimony-doped tin oxide to formaldehyde catalytic oxidation has not been reported.
Disclosure of Invention
Aiming at the problems, the invention provides an antimony-doped tin oxide-manganese oxide composite catalyst capable of catalyzing and oxidizing formaldehyde at room temperature, and a preparation method and application thereof.
In a first aspect, the present invention provides an antimony-doped tin oxide-manganese oxide composite catalyst comprising antimony-doped tin oxide and manganese oxide.
According to the invention, the photo-thermal material antimony-doped tin oxide is compounded with the catalytic active component manganese oxide, so that the photo-thermal effect of the antimony-doped tin oxide can be utilized to effectively convert the absorbed light energy into heat energy, and the redox activity of the material is enhanced, thereby improving the catalytic activity of the material.
Preferably, the mass ratio of antimony-doped tin oxide to manganese oxide is 1: (0.5 to 10).
Preferably, the antimony doped tin oxide is antimony doped tin oxide nanoparticles. The antimony-doped tin oxide nanoparticles not only have strong near infrared light absorption capacity, but also have small particle size, and are not easy to cover active sites on the catalyst.
Preferably, the manganese oxide is a manganese oxide nanowire or a manganese oxide nanosheet.
Preferably, the manganese oxide nanowires and the manganese oxide nanoplatelets are interconnected into a network-like structure in which antimony-doped tin oxide nanoparticles are uniformly dispersed.
Preferably, the size of the antimony-doped tin oxide nanoparticles is 5-10 nm.
Preferably, the diameter of the manganese oxide nanowire is 1-20 nm, the length of the manganese oxide nanowire is 0.2-5 mu m, and the sheet diameter of the manganese oxide nanosheet is 0.5-5 nm.
In a second aspect, the present invention provides a method for preparing an antimony-doped tin oxide-manganese oxide composite catalyst, comprising the steps of:
carrying out hydrothermal reaction on the mixed solution in which the antimony-doped tin oxide, the high-valence manganese source and the reducing agent are uniformly dispersed, and then separating out solids to obtain the antimony-doped tin oxide-manganese oxide composite catalyst.
The antimony-doped tin oxide-manganese oxide composite catalyst directly prepared by using an in-situ composite hydrothermal method has the advantages of simple process, non-toxic and harmless raw materials, low price and easy obtainment, convenient and feasible operation, realization of large-scale industrial production and good repeatability.
Preferably, the hydrothermal reaction temperature is 80-200 ℃ and the reaction time is 4-18 hours.
Preferably, the molar ratio of the high-valence manganese source to the reducing agent is 1: (0.5-2).
Preferably, the source of high valence manganese is potassium permanganate and the reducing agent is ammonium oxalate and/or oxalic acid.
Preferably, the mass ratio of the antimony-doped tin oxide to the high-valence manganese source is (0.01-0.1): 1.
in a third aspect, the invention provides the use of any one of the antimony-doped tin oxide-manganese oxide composite catalysts described above in the catalytic oxidation of formaldehyde, especially in the catalytic oxidation of formaldehyde at room temperature.
The antimony-doped tin oxide-manganese oxide composite catalyst can completely degrade formaldehyde at the temperature of below 100 ℃ and even below 70 ℃.
The catalytic oxidation of formaldehyde may be carried out at room temperature. The antimony-doped tin oxide-manganese oxide composite catalyst shows excellent formaldehyde catalytic activity at room temperature, and the catalytic efficiency is 47-56%.
The antimony-doped tin oxide-manganese oxide composite catalyst has good stability, and can stabilize the catalytic activity without reducing the catalytic activity for more than 10 hours.
Drawings
FIG. 1 shows MnO prepared in examples 1, 2 and 4 of the present invention2ATO and ATO/MnO2-1X-ray diffraction pattern.
FIG. 2 shows MnO prepared in examples 1 to 6 of the present invention2、ATO、ATO/MnO2-0.5、ATO/MnO2-1、ATO/MnO2-1.5 and ATO/MnO2-0.1 catalytic performance diagram of the catalyst at 25-120 ℃.
FIG. 3 shows MnO obtained in example 1 of the present invention2Scanning electron microscope pictures of the catalyst.
FIG. 4 is a scanning electron microscope image of ATO obtained in example 2 of the present invention after hydrothermal treatment.
FIG. 5 shows ATO/MnO prepared in example 4 of the present invention2-1X-ray energy spectral analysis of a scanning electron micrograph of the catalyst.
FIG. 6 shows MnO prepared according to the present invention2And ATO/MnO2-1 catalytic stability diagram of the catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The antimony-doped tin oxide-manganese oxide composite catalyst (composite catalyst for short) according to an embodiment of the present invention includes antimony-doped tin oxide and manganese oxide.
In the composite catalyst, antimony-doped tin oxide can absorb energy of infrared light in solar energy, and formation of more active oxygen species on the surface of the manganese oxide catalyst is accelerated.
The antimony-doped tin oxide in the composite catalyst may be nano antimony-doped tin oxide, for example, antimony-doped tin oxide nanoparticles.
In a preferred embodiment, the size of the antimony-doped tin oxide nanoparticles is 5-10 nm. At this size the problem of coverage of the manganese oxide surface active sites due to excessive particle size can be avoided.
The manganese oxide in the composite catalyst can be nano manganese oxide, the shapes of the manganese oxide can be nano wires and nano sheets, the nano wires are used as framework supports, the nano sheets which are easy to agglomerate can be dispersed, more active sites on the catalyst are exposed, and therefore the catalytic activity of the catalyst can be improved.
The diameter of the manganese oxide nanowire can be 1-20 nm, and the length can be 0.5-5 μm. The manganese oxide nano-sheet can be used as a framework support in the size, and the easily agglomerated manganese oxide nano-sheet is fully dispersed. The manganese oxide nanowires can be manganese oxide of the manganite type.
The sheet diameter of the manganese oxide nano sheet can be 0.5-5 nm. The surface of the manganese oxide catalyst can generate more active sites in the size, which is beneficial to enhancing the catalytic activity of the catalyst. The manganese oxide nanosheets can be birnessite type manganese oxide.
In some embodiments, an antimony doped tin oxide-manganese oxide composite catalyst includes antimony doped tin oxide nanoparticles and manganese oxide nanowires and manganese oxide nanoplatelets. The manganese oxide nanowires and the manganese oxide nanosheets are connected with each other to form a network structure, and the antimony-doped tin oxide nanoparticles are uniformly dispersed in the network structure, so that absorbed light energy can be converted into heat energy, the heat energy can be well transferred to a manganese oxide material, active oxygen species on the surface of manganese oxide are increased, and the catalytic activity of the catalyst can be improved.
In the composite catalyst, the mass ratio of antimony-doped tin oxide to manganese oxide is preferably 1: (0.5 to 10). In the mass ratio, a proper amount of antimony-doped tin oxide can provide additional heat energy for the active catalytic substance manganese oxide to generate more catalytic power, and can avoid the reduction of the catalyst activity caused by the addition of excessive antimony-doped tin oxide to cover active sites. More preferably, the mass ratio of antimony-doped tin oxide to manganese oxide is preferably 1: (0.5-2), more preferably 1: (1-2).
The antimony doped tin oxide may be one commonly used in the art, wherein SnO2May be in the mass percent of90～99％，Sb2O3The mass percentage of (B) can be 1-10%.
In one embodiment of the present invention, the antimony-doped tin oxide-manganese oxide composite catalyst is prepared by an in-situ hydrothermal method. Hereinafter, a method for preparing the composite catalyst will be described as an example.
And dispersing the antimony-doped tin oxide nanoparticles in water (preferably deionized water) uniformly to obtain an antimony-doped tin oxide dispersion liquid. In the antimony-doped tin oxide dispersion liquid, the concentration of the antimony-doped tin oxide nanoparticles can be 2.5-25 mg/mL. The dispersion means may be ultrasonic, etc. The ultrasonic time can be 10-90 min.
And adding a high-valence manganese source and a reducing agent into the antimony-doped tin oxide dispersion liquid, and uniformly mixing to obtain a mixed liquid. The high valence manganese source may be potassium permanganate. Potassium permanganate can provide high-price manganese, and potassium ions can be doped in the obtained composite catalyst, and the potassium ions have a gain effect on the catalytic activity of the catalyst. The reducing agent can be ammonium oxalate and/or oxalic acid, and the ammonium oxalate and/or oxalic acid can control the form of the manganese oxide, so that the manganese oxide nanowires and the manganese oxide nanosheets are connected with each other to form a network-shaped structure.
The mass ratio of the antimony-doped tin oxide to the high-valence manganese source can be (0.01-0.1): by adjusting the mass ratio, the mass ratio of antimony-doped tin oxide to manganese oxide in the obtained composite catalyst can be adjusted.
The molar ratio of the high-valence manganese source to the reducing agent is preferably 1: (0.5-2), more preferably 1: (0.8 to 1.2).
And putting the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction. Through hydrothermal reaction, manganese oxide with a special network structure can be grown, wherein the manganese oxide nanowire is used as a framework to support and disperse manganese oxide nanosheets, and antimony-doped tin oxide nanoparticles are uniformly dispersed in the network structure, so that heat transfer can be better carried out. The hydrothermal reaction condition is only the condition capable of generating manganese oxide, for example, the hydrothermal reaction temperature can be 80-200 ℃, and the reaction time can be 4-18 h. The catalysts prepared are substantially uniform and exhibit substantially uniform catalytic activity over this temperature and time range.
After the reaction is finished, naturally cooling to room temperature, filtering, washing and drying the obtained suspension to obtain the antimony-doped tin oxide-manganese oxide composite catalyst.
The composite catalyst can completely degrade formaldehyde at a lower temperature, shows excellent formaldehyde catalytic activity at room temperature, can efficiently degrade high-concentration formaldehyde gas at room temperature, and has good stability.
In some embodiments, the performance of the composite catalyst of the present invention in catalyzing the oxidation of formaldehyde was tested by the following method.
The antimony-doped tin oxide-manganese oxide composite catalyst is placed in a quartz fixed bed reactor.
The paraformaldehyde solid in a formaldehyde generator placed at room temperature (for example, 25 ℃) is purged by using air as a carrier gas flow to obtain formaldehyde gas.
And (3) reacting the formaldehyde gas with the antimony-doped tin oxide-manganese oxide composite catalyst at 25-120 ℃ through a fixed bed reactor, and collecting tail gas to detect the formaldehyde content.
The space velocity of the formaldehyde gas can be 30000-cat h)。
The concentration of the formaldehyde gas may be 10-100 ppm.
The antimony-doped tin oxide-manganese oxide composite catalyst with high formaldehyde catalytic activity is prepared by in-situ hydrothermal synthesis, the preparation method is simple and feasible, the conditions are mild and controllable, the required catalyst can be stably prepared, the yield is high, and the catalyst can be prepared in large quantities; the invention avoids using precious metals with scarce resources, thereby greatly reducing the preparation cost of the catalyst; the antimony-doped tin oxide-manganese oxide composite catalyst prepared by the invention has high formaldehyde catalytic activity, and the photo-thermal material antimony-doped tin oxide is applied to the field of formaldehyde catalysis for the first time; the antimony-doped tin oxide-manganese oxide composite catalyst prepared by the invention has high room-temperature catalytic activity and stability, and can keep the catalytic activity for 10 hours without reduction in high-concentration formaldehyde gas.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
preparation of manganese oxide catalyst by hydrothermal method
Dissolving 1.0g of potassium permanganate and 0.8g of ammonium oxalate solid in deionized water, and dissolving for 15min under magnetic stirring at room temperature to obtain a mixed solution; transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate, performing exchange washing on the precipitate for 3 times by using water and absolute ethyl alcohol, and drying at 80 ℃ for 8h to obtain a manganese oxide catalyst (MnO)2)。
As can be seen from FIGS. 1 and 3, MnO was prepared as shown by X-ray diffraction and scanning electron microscope2The catalyst consists of flaky birnessite type manganese oxide and fibrous birnessite type manganese oxide which are mutually connected into a special network structure, and is more favorable for adsorption and catalytic reaction of formaldehyde.
The MnO2The application of the catalyst in catalytic degradation of formaldehyde is realized by the following steps:
1) MnO to be used2The catalyst is placed in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and the MnO2The catalyst reacts at the temperature of 25-120 ℃, and the space velocity is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows the useMnO prepared by the method2The catalyst can completely degrade formaldehyde at 110 ℃, and the catalytic efficiency at room temperature (25 ℃) is 45%.
Example 2
Treatment of antimony-doped tin oxide nanoparticles by hydrothermal method
Antimony-doped tin oxide nanoparticles (available from Shanghai silicate research institute of Chinese academy of sciences, SnO)2：Sb2O39: 1) adding into deionized water, mixing, and ultrasonically dispersing for 30min to obtain mixed solution; and transferring the mixed solution into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate, exchanging and washing the precipitate with water and absolute ethyl alcohol for 3 times, and drying at 70 ℃ for 8h to obtain antimony-doped tin oxide nanoparticles (ATO) treated by a hydrothermal method.
As can be seen from FIGS. 1 and 4, the phases of ATO nanoparticles after hydrothermal treatment were not changed and the size of nanoparticles was 5-10nm as shown by X-ray diffraction and scanning electron microscopy.
The application of the ATO nano-particles in catalytic degradation of formaldehyde is realized by the following steps:
1) placing the ATO nano-particles in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor to react with the ATO nano-particles at the temperature of 25-120 ℃, and the airspeed is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows that the ATO nanoparticles have no significant catalytic activity on formaldehyde in the temperature range of 25-120 ℃.
Example 3:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The preparation method of the antimony-doped tin oxide-manganese oxide composite catalyst specifically comprises the following steps:
1) dispersing 0.3g of antimony-doped tin oxide nanoparticles into 40mL of deionized water, and then performing ultrasonic dispersion for 30min to obtain antimony-doped tin oxide dispersion liquid;
2) adding 1.0g of potassium permanganate and 0.8g of ammonium oxalate solid into the antimony-doped tin oxide dispersion liquid obtained in the step 1), and then magnetically stirring for 15min at room temperature to obtain a mixed solution;
3) putting the mixture obtained in the step 2) into a hydrothermal reaction kettle, and reacting for 12 hours at the temperature of 100 ℃ to obtain a suspension;
4) after the reaction is finished, naturally cooling to room temperature, filtering, washing and drying the obtained suspension to obtain antimony-doped tin oxide-manganese oxide composite catalyst ATO/MnO2-0.5, wherein the mass ratio of antimony-doped tin oxide to manganese oxide is 1: 2 (under the condition, the mass of the manganese oxide prepared without adding antimony-doped tin oxide is 0.6g, and the mass of the catalyst prepared after adding 0.3g of antimony-doped tin oxide is 0.9g, so that the mass ratio of the antimony-doped tin oxide to the manganese oxide is calculated to be 1: 2).
The composite catalyst ATO/MnO2-0.5 application in catalytic degradation of formaldehyde, achieved by the following steps:
1) adding the ATO/MnO2-0.5 in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and reacts with the tin oxide nano-particles at the temperature of 25-120 ℃, and the space velocity is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows that ATO/MnO prepared by the method2The-0.5 composite catalyst can completely degrade formaldehyde at 90 ℃, and the catalytic efficiency at room temperature (25 ℃) is 52%.
Example 4:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The antimony-doped tin oxide-manganese oxide composite catalyst ATO/MnO was prepared in the same manner as in example 3 except that the mass of the antimony-doped tin oxide nanoparticles added was 0.6g2-1, wherein the mass ratio of antimony-doped tin oxide to manganese oxide is 1: 1.
as can be seen from FIGS. 1 and 5, the resulting ATO/MnO was confirmed by X-ray diffraction, scanning electron microscope and X-ray energy spectrum analysis2The-1 catalyst consists of manganese oxide and antimony-doped tin oxide, no other impurity phases being produced. The addition of antimony-doped tin oxide does not change the special network structure of the manganese oxide material, and the Mn, Sn and Sb elements in the catalyst are uniformly distributed, which shows that the antimony-doped tin oxide is uniformly dispersed in the network structure.
The composite catalyst ATO/MnO2-1 application in catalytic degradation of formaldehyde, achieved by the following steps:
1) adding the ATO/MnO2-1 is placed in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and reacts with the tin oxide nano-particles at the temperature of 25-120 ℃, and the space velocity is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows that ATO/MnO prepared by the method2The-1 composite catalyst can completely degrade formaldehyde at 70 ℃, and the catalytic efficiency at room temperature (25 ℃) is 56%.
Example 5:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The antimony-doped tin oxide-manganese oxide composite catalyst ATO/MnO was prepared in the same manner as in example 3 except that the mass of the antimony-doped tin oxide nanoparticles added was 0.9g2-1.5, wherein the mass ratio of antimony-doped tin oxide to manganese oxide is 1.5: 1.
the composite catalyst ATO/MnO2-1.5 application in catalytic degradation of formaldehyde, achieved by the following steps:
1) adding the ATO/MnO2-1.5 in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and reacts with the tin oxide nano-particles at the temperature of 25-120 ℃, and the space velocity is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows that ATO/MnO prepared by the method2The-1.5 composite catalyst can completely degrade formaldehyde at 100 ℃, and the catalytic efficiency at room temperature (25 ℃) is 47%.
Example 6:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The antimony-doped tin oxide-manganese oxide composite catalyst ATO/MnO was prepared in the same manner as in example 3 except that the mass of the antimony-doped tin oxide nanoparticles added was 0.06g2-0.1, wherein the mass ratio of antimony doped tin oxide to manganese oxide is 1: 10.
The composite catalyst ATO/MnO2-0.1 application in catalytic degradation of formaldehyde, achieved by the following steps:
1) adding the ATO/MnO2-0.1 in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and reacts with the tin oxide nano-particles at the temperature of 25-120 ℃, and the space velocity is 60000 mL/(g)cath) And collecting tail gas to detect the content of formaldehyde.
As can be seen from FIG. 2, the catalyst activity test shows that ATO/MnO prepared by the method2The-0.1 composite catalyst can completely degrade formaldehyde at 100 ℃, and the catalytic efficiency at room temperature (25 ℃) is 47%.
Example 7:
the following application methods were used to test MnO separately2And ATO/MnO2-1 catalytic stability at room temperature (25 ℃):
1) MnO to be used2Or ATO/MnO2-1 is placed in a quartz fixed bed reactor;
2) adopting air with the flow rate of 100mL/min as carrier air flow to sweep paraformaldehyde solid in a formaldehyde generator at 25 ℃ to obtain 100ppm formaldehyde gas;
3) the formaldehyde gas passes through a fixed bed reactor and the MnO2Or ATO/MnO2-1 reaction at 25 ℃ and space velocity of 60000 mL/(g)cath) Reacting for 10 hours, collecting tail gas at the same time interval, and detecting the content of formaldehyde.
As can be seen from FIG. 6, the stability test of the catalyst shows that the addition of ATO does not affect the stability of the manganese oxide catalyst, and MnO is added under the condition of high concentration of formaldehyde2And ATO/MnO2-1 can stabilize the catalytic activity without decreasing for as long as 10 hours, but ATO/MnO2The catalytic activity of the-1 composite catalyst is obviously higher than that of MnO alone2A catalyst.
Example 8:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The antimony-doped tin oxide-manganese oxide composite catalyst was prepared in the same manner as in example 3 except that the hydrothermal reaction temperature was 80 ℃ and the reaction time was 18 hours, and the obtained results were substantially the same as in example 3.
Example 9:
the antimony-doped tin oxide-manganese oxide composite catalyst comprises antimony-doped tin oxide nanoparticles, manganese oxide nanowires and manganese oxide nanosheets.
The antimony-doped tin oxide-manganese oxide composite catalyst was prepared in the same manner as in example 3 except that the hydrothermal reaction temperature was 200 ℃ and the reaction time was 4 hours, and the obtained results were substantially the same as in example 3.
Claims (10)
1. The antimony-doped tin oxide-manganese oxide composite catalyst is characterized by comprising antimony-doped tin oxide and manganese oxide.
2. The antimony-doped tin oxide-manganese oxide composite catalyst according to claim 1, wherein the mass ratio of antimony-doped tin oxide to manganese oxide is 1: (0.5 to 10).
3. The antimony-doped tin oxide-manganese oxide composite catalyst according to claim 1 or 2, wherein the antimony-doped tin oxide is antimony-doped tin oxide nanoparticles, and the manganese oxide is manganese oxide nanowires and manganese oxide nanosheets, wherein the manganese oxide nanowires and the manganese oxide nanosheets are interconnected to form a network structure, and the antimony-doped tin oxide nanoparticles are uniformly dispersed in the network structure.
4. The antimony-doped tin oxide-manganese oxide composite catalyst according to claim 3, wherein the size of the antimony-doped tin oxide nanoparticles is 5-10nm, the diameter of the manganese oxide nanowires is 1-20 nm, the length of the manganese oxide nanowires is 0.2-5 μm, and the sheet diameter of the manganese oxide nanosheets is 0.5-5 nm.
5. A method of preparing the antimony-doped tin oxide-manganese oxide composite catalyst of any one of claims 1 to 4, comprising the steps of:
carrying out hydrothermal reaction on the mixed solution in which the antimony-doped tin oxide, the high-valence manganese source and the reducing agent are uniformly dispersed, and then separating out solids to obtain the antimony-doped tin oxide-manganese oxide composite catalyst.
6. The method according to claim 5, wherein the hydrothermal reaction temperature is 80 to 200 ℃ and the reaction time is 4 to 18 hours.
7. The method according to claim 5 or 6, wherein the high-valence manganese source is potassium permanganate, the reducing agent is ammonium oxalate and/or oxalic acid, and the molar ratio of the high-valence manganese source to the reducing agent is preferably 1: (0.5-2).
8. The preparation method according to any one of claims 5 to 7, wherein the mass ratio of antimony-doped tin oxide to potassium permanganate is (0.01-0.1): 1.
9. use of the antimony-doped tin oxide-manganese oxide composite catalyst of any one of claims 1 to 4 in the catalytic oxidation of formaldehyde.
10. Use according to claim 9, characterized in that the catalytic oxidation of formaldehyde is carried out at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910392081.7A CN111921522A (en) | 2019-05-13 | 2019-05-13 | Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910392081.7A CN111921522A (en) | 2019-05-13 | 2019-05-13 | Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111921522A true CN111921522A (en) | 2020-11-13 |
Family
ID=73282543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910392081.7A Pending CN111921522A (en) | 2019-05-13 | 2019-05-13 | Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111921522A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112984503A (en) * | 2021-02-05 | 2021-06-18 | 中国科学院宁波材料技术与工程研究所 | Electric heating method and system for efficiently catalyzing methane combustion by antimony-doped tin oxide |
| CN113617202A (en) * | 2021-06-30 | 2021-11-09 | 浙江巨化新材料研究院有限公司 | Composite organic gas pollutant purifying agent with infrared thermal effect and preparation method thereof |
| CN115779890A (en) * | 2022-11-16 | 2023-03-14 | 南通大学 | Preparation method of manganese-based electric heating catalyst for toluene purification |
| CN116272962A (en) * | 2023-03-21 | 2023-06-23 | 张永生 | Catalytic material for treating automobile exhaust |
-
2019
- 2019-05-13 CN CN201910392081.7A patent/CN111921522A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112984503A (en) * | 2021-02-05 | 2021-06-18 | 中国科学院宁波材料技术与工程研究所 | Electric heating method and system for efficiently catalyzing methane combustion by antimony-doped tin oxide |
| CN113617202A (en) * | 2021-06-30 | 2021-11-09 | 浙江巨化新材料研究院有限公司 | Composite organic gas pollutant purifying agent with infrared thermal effect and preparation method thereof |
| CN113617202B (en) * | 2021-06-30 | 2024-07-02 | 浙江巨化新材料研究院有限公司 | Composite organic gas pollutant purifying agent with infrared thermal effect and preparation method thereof |
| CN115779890A (en) * | 2022-11-16 | 2023-03-14 | 南通大学 | Preparation method of manganese-based electric heating catalyst for toluene purification |
| CN116272962A (en) * | 2023-03-21 | 2023-06-23 | 张永生 | Catalytic material for treating automobile exhaust |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Im et al. | Review of MXene-based nanocomposites for photocatalysis | |
| CN111921522A (en) | Antimony-doped tin oxide-manganese oxide composite catalyst for catalytic oxidation of formaldehyde at room temperature and preparation method thereof | |
| Fang et al. | Synthesis of Pd/Au bimetallic nanoparticle-loaded ultrathin graphitic carbon nitride nanosheets for highly efficient catalytic reduction of p-nitrophenol | |
| Li et al. | Photo-assisted selective catalytic reduction of NO by Z-scheme natural clay based photocatalyst: Insight into the effect of graphene coupling | |
| CN102728356B (en) | MnO supporting Pt nanoparticles2Catalyst, preparation method and application thereof | |
| CN107754785B (en) | Graphene-manganese oxide composite catalyst for low-temperature catalytic oxidation of formaldehyde and preparation method thereof | |
| CN110639593B (en) | Boron and nitrogen doped carbon porous nanotube coated platinum alloy nanoparticle material catalyst and preparation method and application thereof | |
| CN106975479B (en) | Sea urchin-shaped CeO2-MnO2Process for producing composite oxide catalyst | |
| JP2008251413A (en) | Manufacturing method of metal-oxide carrying carbon | |
| Jia et al. | Synthesis and characterization of Ag/α-Fe2O3 microspheres and their application to highly sensitive and selective detection of ethanol | |
| CN113000046A (en) | Modified manganese-based mullite catalyst for synergistic purification of nitrogen oxides and volatile organic compounds, and preparation method and application thereof | |
| CN113181914B (en) | Transition metal in-situ doped TiO 2 Catalyst, preparation method and application | |
| CN112264040B (en) | Carbon sphere-graphene oxide catalyst and preparation method and application thereof | |
| Chen et al. | Co/S co-doped Mn3O4-based sulfur-oxide nano-flakes catalyst for highly efficient catalytic reduction of organics and hexavalent chromium pollutants | |
| CN102101051B (en) | Method for preparing carbon nano tube supported nano photocatalysis material capable of degrading nitrogen oxides | |
| CN113244961A (en) | Bimetallic CoCu-MOF visible light catalyst and preparation method and application thereof | |
| Duan et al. | The composite of Zr-doped TiO2 and MOF-derived metal oxide for oxidative removal of formaldehyde at the room temperature | |
| Wang et al. | A novel 2D nanosheets self-assembly camellia-like ordered mesoporous Bi12ZnO20 catalyst with excellent photocatalytic property | |
| CN111375411B (en) | Monoatomic Cu/TiO 2 Method for preparing nano-wire | |
| Chen et al. | Advances in photochemical deposition for controllable synthesis of heterogeneous catalysts | |
| WO2024011905A1 (en) | Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof | |
| Yu et al. | Preparation of Au 0.5 Pt 0.5/MnO 2/cotton catalysts for decomposition of formaldehyde | |
| Liu et al. | Novel bimetallic MOF derived N-doped carbon supported Ru nanoparticles for efficient reduction of nitro aromatic compounds and rhodamine B | |
| CN114160148B (en) | Cu-based catalyst for preparing hydrogen by reforming methanol and preparation method and application thereof | |
| CN113751006B (en) | Carbon-coated nickel oxide nanocomposite and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201113 |