CN115028203A - Manganese oxide superfine nano powder containing high-index crystal face oxygen defects and preparation method and application thereof - Google Patents
Manganese oxide superfine nano powder containing high-index crystal face oxygen defects and preparation method and application thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 101
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 85
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001301 oxygen Substances 0.000 title claims abstract description 84
- 239000011858 nanopowder Substances 0.000 title claims abstract description 49
- 239000013078 crystal Substances 0.000 title claims abstract description 34
- 230000007547 defect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 97
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000002159 nanocrystal Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000012286 potassium permanganate Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000012855 volatile organic compound Substances 0.000 claims description 20
- 229960005070 ascorbic acid Drugs 0.000 claims description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims description 19
- 239000011668 ascorbic acid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
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- 238000000227 grinding Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
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- 239000003054 catalyst Substances 0.000 description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018663 Mn O Inorganic materials 0.000 description 2
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- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
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Abstract
The invention relates to manganese oxide superfine nano powder containing high-index crystal face oxygen defects, a preparation method and application thereof, belonging to the field of environmental catalytic materials. The manganese oxide superfine nano powder material is birnessite delta-MnO formed by stacking nano crystal grains 2 A material; the grain size of the nano crystal grains is 15-35 nm; in the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect, the valence state of manganese element is Mn 3+ And Mn 4+ ，Mn 3+ 40-50% of the total content of manganese element, Mn 4+ The manganese oxide accounts for 60 to 50 percent of the total content of the manganese element, and the average oxidation valence state of the manganese is 3.45 to 3.60; the manganese oxide superfine nano powder material containing high index crystal face oxygen defects adsorbs oxygen O on the surface ads Accounts for 30 to 45 percent of the total content of oxygen elements, and oxygen O is adsorbed on the surface ads With surface lattice oxygen O latt The ratio of the contents is 0.45 to 0.5.
Description
Technical Field
The invention belongs to the field of environmental catalytic materials, and particularly relates to manganese oxide superfine nano powder containing high-index crystal face oxygen defects, and a preparation method and application thereof.
Background
At present, O 3 Has become one of the main factors of the exceeding of the urban air quality. Volatile organic compounds VOCs being O-forming 3 The important precursor mainly exists in the original and auxiliary materials or products of enterprises, belongs to toxic and harmful substances, and the strengthening of VOCs treatment is the control of O at the present stage 3 An effective way of contamination.
In recent years, the methods for treating the tail end of organic waste gas mainly include: absorption, adsorption, condensation, membrane separation, regenerative combustion, regenerative catalytic combustion, catalytic combustion and the like. The adsorption technology has the problems of frequent replacement of the adsorbent, unsuitability for high-concentration waste gas, low adsorption efficiency when the waste gas humidity is high, unsuitability for waste gas containing particles, high requirement on waste gas pretreatment and the like; the absorption technology has low purification efficiency and large water consumption, discharges a large amount of waste water, causes pollution transfer and has the problem of equipment corrosion; the direct combustion technology has high operation temperature, high operation cost when treating low-concentration waste gas and high fuel cost when treating low-concentration VOCs.
The catalytic combustion technology (catalytic oxidation technology) has lower operation temperature than direct combustion and high treatment efficiency, and organic waste gas VOCs is heated to more than 250 ℃, and the organic waste gas is oxidized and decomposed into CO at lower temperature under the action of a catalyst 2 And H 2 And O, no secondary pollution is generated. However, in the catalytic combustion technology, the catalyst is easy to deactivate (sintering, poisoning and coking), the price of the common noble metal catalyst is high, and the non-noble metal catalyst is activated when the VOCs are purified at low temperatureLow reactivity, slow reaction rate and the like. Among all non-noble metal catalysts, metal manganese oxides are studied more because of high activity and low toxicity, and manganese has a variable valence state, can show better redox characteristics, and is expected to become a catalyst for efficiently catalyzing and purifying organic waste gas.
Disclosure of Invention
In view of the above, in order to solve the problems of high price of noble metal catalysts used in catalytic oxidation technology and low activity and reaction rate of non-noble metal catalysts for purifying VOCs at low temperature, the invention provides a manganese oxide ultrafine nano powder material which has a large specific surface area and high exposure of active sites, and is beneficial to adsorption, activation and catalytic oxidation of organic waste gases such as toluene and the like.
Specifically, in the first aspect, the invention provides a manganese oxide superfine nano powder material containing high-index crystal face oxygen defects, wherein the manganese oxide superfine nano powder material is birnessite delta-MnO formed by stacking nano crystal grains 2 A material; the grain size of the nano crystal grains is 15-35 nm;
in the manganese oxide superfine nano powder material containing high-index crystal face oxygen defects, the valence state of manganese element is Mn 3+ And Mn 4+ ，Mn 3+ 40-50% of the total content of manganese element, Mn 4+ The manganese oxide accounts for 60-50% of the total content of manganese elements, and the average oxidation state of manganese is 3.45-3.60;
the surface of the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect adsorbs oxygen O ads Accounts for 30 to 45 percent of the total content of oxygen elements, and oxygen O is adsorbed on the surface ads With surface lattice oxygen O latt The ratio of the contents is 0.45 to 0.5.
Preferably, the specific surface area of the manganese oxide superfine nano powder material containing high-index crystal face oxygen defects is 220-250m 2 /g。
In a second aspect, the invention provides a preparation method of the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect, and the preparation method comprises the following steps:
respectively preparing a potassium permanganate solution and an ascorbic acid solution, and controlling the molar ratio of the use amount of potassium permanganate to the use amount of ascorbic acid to be 1: 0.125-1;
transferring the potassium permanganate solution into an ultrasonic cleaning machine, and dropwise adding an ascorbic acid solution into the potassium permanganate solution under an ultrasonic condition to carry out ultrasonic-assisted reaction;
centrifuging and washing the mixed solution after the ultrasonic treatment to obtain a solid product, and freeze-drying the solid product in a freeze dryer; grinding and collecting the product to obtain the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect.
Preferably, the power of the ultrasound is 100 to 500W.
Preferably, the reaction time under the assistance of the ultrasound is 30-120 min.
Preferably, the speed of dropwise addition is 0.5-1.5 mL/min.
In a third aspect, the invention provides an application of the manganese oxide ultrafine nano powder material containing high-index crystal face oxygen defects in low-temperature catalytic oxidation purification of a volatile organic compound, wherein the volatile organic compound comprises at least one of toluene, benzene and formaldehyde.
Advantageous effects
(1) The preparation method provided by the invention is simple, has few steps, short time consumption and cheap raw materials, and is easy to realize industrial production;
(2) the birnessite type manganese oxide nano powder material obtained by the invention has large specific surface area, and is rich in (110) and (310) high-index crystal faces, surface oxygen vacancies and Mn 4+ The active site has high exposure degree, and is beneficial to contact, adsorption and catalytic oxidation of the material with gases such as oxygen, toluene and the like;
(3) the nano powder material provided by the invention can realize the treatment of low-concentration VOCs waste gas in medium and small air volume, has high purification efficiency (more than or equal to 99%), low ignition point temperature and lasting stability, and has great application potential in the treatment of volatile organic compounds in the petrochemical industry.
Drawings
FIG. 1 shows MnO prepared in example 1 x -AA US Sem (a), tem (b), hrtem (c) and xrd (d) characterization plots of the materials;
FIG. 2 shows MnO prepared in example 1 x -AA US A nitrogen adsorption-desorption isothermal curve chart of the material;
FIG. 3 shows MnO prepared in example 1 x -AA US XPS and EPR characterization diagrams of materials Mn3s, Mn2p and O1 s;
FIG. 4 shows MnO prepared in example 1 x -AA US Hydrogen temperature programmed reduction of materials (H) 2 -TPR) spectrum;
FIG. 5 shows MnO prepared in example 1 x -AA US Oxygen temperature programmed desorption (O) of materials 2 -TPD) spectrum;
FIG. 6 shows MnO synthesized in example 1 x- AA US A comparative graph of the catalytic performance of the catalyst under different toluene concentrations;
FIG. 7 shows MnO synthesized in example 1 x- AA US A catalytic stability test schematic diagram of the catalyst at 200 ℃;
FIG. 8 shows MnO synthesized in example 1 x- AA US Catalyst and MnOx-AA synthesized in comparative example 1 stir MnOx-AA synthesized in comparative example 2 H Comparative graph of catalytic performance at the same toluene concentration.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative, and not restrictive, of the invention.
The invention provides a manganese oxide superfine nano powder material containing high-index crystal face oxygen defects and capable of being applied to catalytic oxidation and purification of VOCs with low concentration (such as less than 1000ppm) and a preparation method thereof. The manganese oxide superfine nano powder material is formed by stacking fine nano crystal grains, a large number of oxygen defects exist on the surfaces of the grains, and the exposure degree of active sites is high. The grain size of the nano crystal grains is 15-35 nm.
In the invention, the manganese oxide superfine nano powder material is birnessite delta-MnO 2 The material is weakly crystalline. Wherein the valence state of the manganese element is Mn 3+ And Mn 4+ ，Mn 3+ 40-50% of the total content of manganese element, Mn 4+ Accounts for 60 to 5 percent of the total content of the manganese element0% and the Average Oxidation State (AOS) of manganese is between 3.45 and 3.60. To maintain the overall charge balance of the material, the manganese dioxide surface is often accompanied by the generation of oxygen vacancies. The surface of the manganese oxide nano powder material adsorbs oxygen O ads Accounts for 30 to 45 percent of the total content of oxygen elements, and oxygen O is adsorbed on the surface ads With surface lattice oxygen O latt The content ratio is 0.45-0.5.
δ-MnO 2 Is in a two-dimensional lamellar structure, each layer is composed of Mn-O octahedrons, and H is filled between layers + 、K + And the like. The Mn-O lamellar structure can expose more catalytic active sites and can generate oxygen vacancies more easily. And the more oxygen vacancies that are the primary active sites, the higher the catalytic oxidation performance of the material. Therefore, the birnessite delta-MnO provided by the invention 2 The material has higher catalytic activity than other types of manganese dioxide materials.
At the same time, delta-MnO 2 Mn in (1) 3+ And Mn 4+ The content is related to the oxygen vacancy concentration, the higher the oxygen vacancy content, the more Mn is needed to maintain charge balance 3+ The higher the content tends to be; meanwhile, Mn 3+ The higher the content, which also means that the material has a high content of oxygen vacancies, the higher the catalytic activity of the material. The surface adsorbed oxygen of the manganese dioxide catalytic material provided by the invention is also related to the concentration of oxygen vacancies, and the higher the surface adsorbed oxygen content is, the higher the content of the oxygen vacancies is, and the higher the catalytic activity of the material is.
The manganese oxide superfine nano powder material has higher specific surface area. In some embodiments, the specific surface area of the manganese oxide ultrafine nano powder material can reach 220-250m 2 /g。
The preparation method of the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect provided by the invention is exemplarily illustrated below, and mainly comprises the following steps.
First, an oxidizing raw material potassium permanganate is dissolved in water to form a potassium permanganate solution, and a reducing raw material ascorbic acid is dissolved in water to form an ascorbic acid solution. In some embodiments, the molar ratio of the potassium permanganate to the ascorbic acid can be controlled to be 1:0.125-1, preferably 1:0.25. When the molar ratio of the two is less than 1:1, manganese oxalate is generated, and birnessite delta-MnO containing a large number of crystal plane oxygen defects cannot be directly obtained 2 A material; when the molar ratio of the two is more than 1: when the reaction time is 0.125, potassium permanganate cannot completely react, so that the waste of the added raw materials is caused.
Then, transferring the potassium permanganate solution into an ultrasonic cleaning machine with ultrasonic power of 100-; under the ultrasonic condition, the ascorbic acid solution is dropwise added into the potassium permanganate solution, and the dropwise adding speed can be controlled to be 0.5-1.5 mL/min. In some embodiments, the time for the reaction with the assistance of ultrasound may be 30-120 min.
The ultrasonic mode can enhance the diffusion of substances in the reaction process, so that the obtained particles are more uniform. The obtained material particles are too small and difficult to separate due to the over-high power or over-long time of ultrasound, and the high-index crystal face cannot be obtained due to the poor crystallinity; when the power is too weak or the time is too short, the material particles will grow gradually, the surface area will decrease, the oxygen vacancy content will also decrease, and finally the catalytic performance of the material will decrease.
In the process of synthesizing the manganese dioxide material by the ultrasonic-assisted method, energy can be provided for the redox reaction of the raw materials by applying ultrasonic with certain power, so that the crystal lattice of the manganese dioxide material product grows in disorder and generates distortion while growing, and finally, the manganese dioxide ultrafine nano powder material with poor crystallinity and more defect active sites is obtained.
And finally, centrifuging and washing the mixed solution after the ultrasonic treatment to obtain a solid product, and freeze-drying in a freeze dryer. Grinding and collecting the product to obtain brown-black manganese oxide superfine nano powder material MnO x -AA US 。
In some embodiments, the preparation of the manganese oxide ultrafine nano powder material can also be carried out by adopting a stirring auxiliary method or a hydrothermal auxiliary method.
And (3) synthesizing the manganese oxide nano powder material under the assistance of stirring. Dissolving potassium permanganate in water, and adding polyhydroxy compound ascorbic acid solution with strong reducibility into the high manganese under continuous stirringPotassium solution. In some embodiments, the molar ratio of the ascorbic acid to potassium permanganate used may be in the range of 0.125 to 1: 1. preferably, the rotating speed of the stirring is 300-600 revolutions per minute. Reacting for 1-5 h at room temperature, centrifuging, washing with water, and freeze-drying in a freeze dryer. Grinding and collecting the product to obtain brown black manganese oxide superfine nano powder material MnO x -AA stir 。
And (3) synthesizing the manganese oxide nano powder material under the assistance of hydrothermal. The mixed solution of the ascorbic acid and the potassium permanganate with the molar ratio of 0.125-1:1 is stirred uniformly at room temperature and then added into a reaction kettle to react for 8-24h in an oven at the temperature of 80-140 ℃. The reaction temperature and time are controlled, so that the generated material can be prevented from being too high in aging degree, and the good catalytic activity of the material can be guaranteed. After the reaction is finished, the reaction product is naturally cooled to room temperature. Centrifuging, washing with water, and lyophilizing in a lyophilizer. Grinding and collecting the product to obtain brown black manganese oxide superfine nano powder material MnO x -AA H 。
The manganese oxide superfine nano powder materials synthesized by an ultrasonic auxiliary method, a stirring auxiliary method and a hydrothermal auxiliary method have consistent crystal forms, but have differences in lattice distortion degree, oxygen vacancy and the like, so that the properties of the powder materials are changed. Wherein, the ultrafine powder material obtained by the ultrasonic-assisted method has obviously more excellent catalytic performance.
The manganese oxide superfine nano powder material containing high-index crystal face oxygen defects, prepared by the invention, solves the problems of low-temperature activity and low reaction rate of the existing VOCs purification catalyst. Meanwhile, the material has larger specific surface area, high surface oxygen vacancy and active site exposure degree, moderate density ratio, strong oxidation-reduction capability and easy adsorption and activation of VOCs molecules and O 2 Molecule, etc.
When the manganese oxide superfine nano powder material is used as a catalyst for efficiently catalyzing and oxidizing low-concentration VOCs at a lower temperature, the manganese oxide superfine nano powder material is added into a fixed bed continuous flow reactor for performance test, and the space velocity is 60000mL g -1 h -1 Reacting toluene C in the inlet and outlet gases 7 H 8 Concentration deviceAnd performing online detection by gas chromatography. Preferably, MnO x -AA US The material has higher C 7 H 8 Catalytic oxidation activity: for 600ppm of C 7 H 8 Can realize the removal conversion rate of more than 90 percent under the low temperature condition of 160-170 ℃; when the temperature is increased to 200 ℃, the material can continuously realize C for at least 40 hours 7 H 8 Removal conversion rate of more than 99%.
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., a person skilled in the art can make a selection within suitable ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Dissolving 1.58g (0.01mol) of potassium permanganate in 45mL of water, dissolving 0.44g (0.0025mol) of ascorbic acid in 5mL of water, then transferring the beaker containing the potassium permanganate solution to an ultrasonic cleaning machine with the ultrasonic power of 500W, dropwise adding the ascorbic acid solution into the potassium permanganate solution at the dropwise adding speed of 1mL/min, and reacting for 60 min. Centrifuging, washing with water, and lyophilizing in a lyophilizer. Grinding and collecting the product to obtain a brownish black manganese oxide nano powder material, and naming the obtained sample as MnO x- AA US 。
The manganese oxide nano material MnO is characterized by a scanning electron microscope, a transmission electron microscope, a high-resolution transmission electron microscope, X-ray diffraction, nitrogen adsorption-desorption, X-ray photoelectron spectroscopy and chemical adsorption x- AA US Chemical composition and chemical microenvironment.
FIG. 1 shows MnO prepared in example 1 x -AA US Sem (a), tem (b), hrtem (c) and xrd (d) characterization of the materials. As can be seen from the figure, the material has no definite morphology and is formed by stacking fine nanoparticles. HRTEM photograph displayThe direction of the shown lattice stripes is complicated, and the material is proved to have a large number of surface defects and high exposure degree of active sites. From HRTEM pictures
And
the lattice fringes and the weak and wide diffraction peaks at 36.5 degrees and 65.5 degrees in an XRD pattern show that the material is birnessite delta-MnO rich in (110) and (310) high-index crystal planes and has a large number of defects on the high-index crystal planes 2 A material.
FIG. 2 shows MnO prepared in example 1 x -AA US Nitrogen adsorption-desorption isotherm plot of the material. As can be seen in the figure, MnO preparation using the ultrasound-assisted method x -AA US The material has a large specific surface area of about 235.4m 2 (ii) in terms of/g. Because the material is mainly formed by stacking fine nano crystal grains (15-35nm), the large specific surface area is favorable for the catalyst material to be in full contact with VOCs gases such as toluene and the like, and more active sites are provided to participate in adsorption reaction.
FIG. 3 shows MnO prepared in example 1 x -AA US XPS and EPR characterization diagrams of materials Mn3s, Mn2p and O1 s. As can be seen from the figure, Mn 3+ About 47.9% of manganese element, oxygen vacancy generation and surface adsorption of oxygen O are accompanied in order to maintain the overall charge balance of the material ads With surface lattice oxygen O latt The ratio of 0.48 also indicates the presence of oxygen vacancies. MnO x -AA US The Average Oxidation State (AOS) of medium manganese can be calculated according to the energy level difference of Mn3s in XPS, and MnO can be obtained by empirical formula AOS (8.956-1.126) xDelta E x -AA US Mn3s with a binding energy split level difference of 4.79eV, corresponding to an average oxidation state of Mn of 3.56. O is ads /O latt In relation to the oxygen vacancy content, which increases with increasing oxygen vacancy content, MnO x -AA US Catalyst O ads /O latt Is 0.48, is common with the symmetric EPR signal observed at g-2.001Reflect MnO x -AA US Concentration of oxygen vacancies in the catalyst, meaning MnO x -AA US The oxygen vacancy on the surface of the catalyst promotes the adsorption and activation of gas-phase oxygen molecules, and simultaneously, enough easily reduced Mn is also present on the surface 4+ Absorbing and activating VOCs molecules such as toluene and the like to realize low-temperature catalytic combustion reaction.
FIG. 4 shows MnO prepared in example 1 x -AA US Hydrogen temperature programmed reduction of materials (H) 2 TPR) spectrum.
As can be seen from the figure, MnO is consumed x -AA US The reduction peak temperature of the oxygen adsorbed on the surface of the catalyst is 174 ℃, and MnO is x -AA US Middle Mn 4+ Has a reduction peak temperature of 235 ℃ which is lower than that of the manganese oxide catalyst reported in the prior literature, and the whole reduction process is too fast to separate the reduction peaks, which indicates that MnO is not available x -AA US The redox performance of the catalyst is greatly improved, the movement capability of lattice oxygen is accelerated, and the lattice oxygen is promoted to be removed to participate in the reaction. Thus, MnO can be inferred x -AA US The material has stronger catalytic oxidation performance of VOCs such as toluene and the like.
FIG. 5 shows MnO prepared in example 1 x -AA US Oxygen temperature programmed desorption (O) of materials 2 -TPD) spectrum. As can be seen from the figure, the surface active oxygen species and oxygen transport properties of the manganese oxide catalyst vary. At low temperature (below 300 deg.C), MnO x -AA US A lower amount of desorption of surface-adsorbed oxygen indicates a lower surface oxygen vacancy concentration, while a lower initial deoxidation temperature (107 ℃) indicates MnO x -AA US The oxygen vacancy on the surface of the catalyst is easy to activate gas-phase oxygen molecules and the formed surface chemically adsorbed oxygen is easy to desorb to participate in catalytic combustion reaction. Compared with the sharp oxygen desorption peak of the prior manganese oxide catalyst at a certain temperature, MnO x -AA US The desorption peaks of the oxygen adsorbed on the surface of the catalyst and the oxygen on the surface crystal lattice have no clear limit and are represented as continuous and broad desorption peaks, which shows that the material has low crystallinity, and the crystal lattice exposed on the surface is very disordered, thereby providing an opportunity for the rapid movement of the oxygen on the surface crystal lattice. Therefore, the number of the first and second electrodes is increased,MnO x -AA US oxygen vacancy concentration at the surface of the catalyst and Mn adjacent to the oxygen vacancies 4+ The reducibility of (A) is an important index for improving the catalytic activity.
MnO synthesized in example 1 x- AA US The catalyst is subjected to a toluene low-temperature degradation performance test in a fixed bed continuous flow reactor. A quartz tube with the inner diameter of 8mm is used as a reactor, the filling amount of the catalyst is 0.1g, and the reaction inlet gas is as follows: c 7 H 8 The concentration is 600/800/1000ppm, O 2 Concentration 21% carrier gas N 2 The reaction temperature is 140-320 ℃, and the space velocity is 60000mL g -1 h -1 Inlet and outlet of the reactor C 7 H 8 The concentration was measured on-line by gas chromatography. Catalyst reactivity through C 7 H 8 The conversion of (b) is expressed.
FIG. 6 shows MnO synthesized in example 1 x- AA US The catalytic performance of the catalyst at different toluene concentrations is compared. As can be seen from the figure, MnO x- AA US Catalyst in C 7 H 8 At a concentration of 600ppm, the reaction temperatures T50 and T90 for 50% and 90% conversion of toluene were 146 and 163 ℃ respectively. MnO with increasing toluene concentration x- AA US The catalytic activity of the catalyst is slightly reduced, and when the toluene concentration reaches 1000ppm, the complete conversion temperature of toluene is about 15 ℃ higher than that of 600ppm, but MnO is higher than that of 1000ppm x- AA US The catalyst still has higher catalytic activity.
FIG. 7 shows MnO synthesized in example 1 x- AA US The catalyst stability at 200 ℃ is schematically tested. As can be seen from the figure, MnO was within 40 hours x- AA US The conversion rate of the catalyst for removing the toluene is kept above 99 percent, and no obvious attenuation is shown.
As can be seen from FIGS. 6 and 7, for 600ppm of C 7 H 8 More than 90% removal conversion can be achieved at 163 ℃. After raising the temperature to 200 ℃, the material can continuously realize C for at least 40 hours 7 H 8 Removal conversion rate of more than 99%.
Example 2
Essentially the same as the protocol of example 1, with the main differences that: the amount of ascorbic acid used in this example was 0.22 g.
Comparative example 1
And (3) synthesizing the manganese oxide nano powder material under the assistance of stirring. 1.58g (0.01mol) of potassium permanganate are dissolved in 45mL of water, and 0.44g (0.0025mol) of ascorbic acid is dissolved in 5mL of water. The ascorbic acid solution was added to the potassium permanganate solution with constant stirring at 400 rpm. The reaction was carried out at room temperature for 3 h. Centrifuging, washing with water, and lyophilizing in a lyophilizer. Grinding and collecting the product to obtain brown-black manganese oxide powder material named as MnO x -AA stir 。
Comparative example 2
And (3) synthesizing the manganese oxide nano powder material under the assistance of hydrothermal. 1.58g (0.01mol) of potassium permanganate was dissolved in 45mL of water, 0.44g (0.0025mol) of ascorbic acid was dissolved in 5mL of water, and the two solutions were mixed and stirred well at room temperature, then added to a reaction vessel and reacted in an oven at 100 ℃ for 12 hours. After the reaction is finished, the reaction product is naturally cooled to room temperature. Centrifuging, washing with water, and lyophilizing in a lyophilizer. Grinding and collecting the product to obtain brown black manganese oxide powder material named as MnO x -AA H 。
FIG. 8 shows MnO synthesized in example 1 x- AA US Catalyst and MnOx-AA synthesized in comparative example 1 stir MnOx-AA synthesized in comparative example 2 H Comparative graph of catalytic performance at the same toluene concentration. As can be seen from FIG. 8, MnO x All have a certain C 7 H 8 Catalytic oxidation active, and MnO x- AA US To C 7 H 8 The catalytic oxidation performance is obviously superior to other MnO x And (3) sampling.
The following table shows the performance parameters of the manganese oxide ultrafine nano powder materials prepared in the above examples 1-2 and comparative examples 1-2:
wherein, T 90 A toluene conversion of 600ppm reached a temperature of 90%.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (7)
1. The manganese oxide superfine nano powder material containing high-index crystal face oxygen defects is characterized in that the manganese oxide superfine nano powder material is birnessite delta-MnO formed by stacking nano crystal grains 2 A material; the grain size of the nano crystal grains is 15-35 nm;
in the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect, the valence state of manganese element is Mn 3+ And Mn 4+ ，Mn 3+ 40-50% of the total content of manganese element, Mn 4+ The manganese oxide accounts for 60-50% of the total content of manganese elements, and the average oxidation state of manganese is 3.45-3.60;
the surface of the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect adsorbs oxygen O ads Accounts for 30 to 45 percent of the total content of oxygen elements, and oxygen O is adsorbed on the surface ads With surface lattice oxygen O latt The ratio of the contents is 0.45 to 0.5.
2. The manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect as claimed in claim 1, wherein the specific surface area of the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect is 220-250m 2 /g。
3. The preparation method of the manganese oxide superfine nano powder material containing the high-index crystal plane oxygen defect as claimed in claim 1 or 2, characterized in that the preparation method comprises the following steps:
respectively preparing a potassium permanganate solution and an ascorbic acid solution, and controlling the molar ratio of the potassium permanganate to the ascorbic acid to be 1: 0.125-1;
transferring the potassium permanganate solution into an ultrasonic cleaning machine, and dropwise adding an ascorbic acid solution into the potassium permanganate solution under an ultrasonic condition to carry out ultrasonic-assisted reaction;
centrifuging and washing the mixed solution after the ultrasonic treatment to obtain a solid product, and freeze-drying the solid product in a freeze dryer; grinding and collecting the product to obtain the manganese oxide superfine nano powder material containing the high-index crystal face oxygen defect.
4. The preparation method according to claim 3, wherein the power of the ultrasound is 100 to 500W.
5. The preparation method according to claim 3 or 4, wherein the reaction time under the assistance of the ultrasound is 30-120 min.
6. The method according to any one of claims 3 to 5, wherein the rate of the dropwise addition is 0.5 to 1.5mL/min and the rate of the dropwise addition is 0.5 to 1.5 mL/min.
7. The application of the manganese oxide superfine nano-powder material containing the high-index crystal face oxygen defect in low-temperature catalytic oxidation purification of a volatile organic compound according to claim 1 or 2, wherein the volatile organic compound comprises at least one of toluene, benzene and formaldehyde.
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