CN116328802B - Preparation method of beta-FeOOH@MXene nanocomposite catalyst - Google Patents
Preparation method of beta-FeOOH@MXene nanocomposite catalyst Download PDFInfo
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- CN116328802B CN116328802B CN202111527018.3A CN202111527018A CN116328802B CN 116328802 B CN116328802 B CN 116328802B CN 202111527018 A CN202111527018 A CN 202111527018A CN 116328802 B CN116328802 B CN 116328802B
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- mxene
- feooh
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- ferric chloride
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- 229910003153 β-FeOOH Inorganic materials 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002114 nanocomposite Substances 0.000 title claims description 8
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 19
- 229940032296 ferric chloride Drugs 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 12
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000002086 nanomaterial Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000009939 endogenous nitrosation Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LECSHJWIACEDPZ-UHFFFAOYSA-N ethane-1,2-diamine naphthalene hydrochloride Chemical compound C(CN)N.C1=CC=CC2=CC=CC=C12.Cl LECSHJWIACEDPZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The invention discloses a method for synthesizing beta-FeOOH@MXene composite catalyst powder. The preparation method comprises the following steps: 1) Etching Ti with hydrofluoric acid 3 AlC 2 The powder is subjected to high-power ultrasonic and centrifugal treatment to prepare MXene few-layer dispersion liquid; 2) FeCl is added 3 Adding the solution into the MXene prepared in the step 1), and fully stirring and uniformly mixing; 3) Pouring the mixed solution in the step 2) into a hydrothermal kettle, preparing beta-FeOOH@MXene hybrid nano particles by adopting a one-step hydrothermal method, and obtaining the final catalyst powder after vacuum suction filtration, washing and vacuum drying. The catalyst prepared by the method has high catalytic oxidation efficiency on nitrite, and can well solve the problem of UV-heat/H 2 O 2 Comprehensive method of oxidation combined with dual-zone absorption to cooperatively remove SO 2 And NO x Residual NO in the waste liquid at the tail part of the reaction tower 2 ‑ The problems are that the treatment flow is simple, no additional energy is consumed, the effect is stable, the treatment can be recycled for multiple times, and the treatment method has good effectEnvironmental benefit and economic benefit, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and catalytic function preparation, and particularly relates to a method for synthesizing a catalyst for efficiently catalyzing and oxidizing nitrite and application thereof.
Background
Along with the development of industry and the improvement of living standard of people, the demand for energy is also increasing continuously, and coal is still used as main energy to be consumed in the current energy structure and power structure in China. The coal-fired flue gas contains various harmful pollutants including SO 2 、NO x And the like, which cause extremely serious harm to the atmospheric environment.
Based on the problems of high operation cost, variable flue gas conditions and the like of industrial boilers and melting furnaces, the method is developed and applicable to low-load industrial boilers in recent years, and can cooperatively remove SO 2 And an economical and efficient method of NOx. The method consists of three parts: 1) Initial absorber use NH 4 OH Pre-absorption SO 2 The method comprises the steps of carrying out a first treatment on the surface of the 2) By UV-heat/H 2 O 2 A hybrid catalytic reactor for oxidizing NO: (3) By means of (NH) 4 ) 2 SO 3 Absorption of generated NO using a primary absorber 2 Obtain the main product of NH 4 NO 2 And (NH) 4 ) 2 SO 4 . Due to the front end (NH 4 ) 2 SO 3 The use of an absorbent, the process eventually generates a large amount of NO 2 - (. About.400 mg/L) results in high toxicity and high instability of the wastewater. In 2017, the world health organization international cancer research institute has listed nitrites ingested under conditions that result in endogenous nitrosation in the class 2A carcinogen list. Nitrite food poisoning can cause blackmouth disease, methemoglobin and the like, and becomes a major cause of harm to human health. Nitrite in treated water becomes a hot spot problem in recent years because nitrite appearing at the rear end of a denitration and desulfurization process cannot be well solved.
Disclosure of Invention
For current UV-heat/H 2 O 2 Oxidative combined dual zone absorption integrated process to synergistically remove SO 2 And NO remaining in tail waste liquid in NOx reaction tower 2 - The invention aims to synthesize a method capable of rapidly synthesizing NH 4 NO 2 Conversion to NH 4 NO 3 The novel nano composite material catalyst reduces the toxicity of water; and moreover, the leaching rate of the catalyst surface active particles is strictly controlled, so that secondary pollution of the water body is avoided. Upon completion of NO 2 - After the oxidation process, (NH) at the bottom of the column 4 ) 2 SO 4 -NH 4 NO 3 And (3) dehydrating, evaporating and crystallizing to obtain the compound fertilizer, so that the sustainable development of green economy is realized. The preparation method of the catalyst comprises the following steps: preparation of MXene few-layer dispersion liquid, preparation of beta-FeOOH@MXene composite nano material and application of beta-FeOOH@MXene composite film.
The first aim of the invention is to provide a preparation method of the catalyst with high-efficiency catalytic oxidation of nitrite, which has simple process, is nontoxic and environment-friendly, and is suitable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a catalyst for efficiently catalyzing and oxidizing nitrite comprises the following steps:
1) Preparation of MXene few layer dispersion: 2g of lithium fluoride was added to 40mL of hydrochloric acid solution, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Stirring the mixture in the solution for 24 hours; after the pH of the supernatant is higher than 6 through ultrasonic centrifugation for many times, adding 40mL of ethanol into the precipitate, and carrying out ultrasonic treatment for 1h to obtain an MXene few-layer nano-sheet; centrifuging the solution, and collecting a few-layer dispersion liquid;
2) Preparation of 0.9M ferric chloride solution: weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark;
dispersing the ferric chloride solution prepared in the step 2) into the MXene few-layer dispersion liquid prepared in the step 1), stirring and dispersing, and pouring the mixture into a reaction kettle for hydrothermal treatment; and centrifuging, washing and drying the product to obtain the beta-FeOOH@MXene composite powder.
Further, the concentration of hydrochloric acid in the step 1) is 9mol/L, the stirring temperature is 30-35 ℃, the rotating speed is 450r/min, and the etching time is 24-48 h.
Further, the ultrasonic power in the step 1) is 750W, and the centrifugal rotating speed is 3500-5000 r/rnin.
Further, the hydrothermal temperature in the step 3) is 150 ℃, and the hydrothermal time is 12 hours.
Further, the mass ratio of the ferric chloride to the MXene in the step 1) is 1:0.1-0.3.
The second object of the invention is to provide a catalyst with high-efficiency catalytic oxidation of nitrite, which is prepared by the method.
The third object of the invention is to provide the application of the catalyst with high-efficiency catalytic oxidation of nitrite prepared by the method in catalytic oxidation of sodium nitrite.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention prepares a catalyst with high-efficiency catalytic oxidation nitrite, which has a nano rod-shaped structure, and beta-FeOOH and MXene active sites are uniformly distributed on the surface of the catalyst.
2) In the invention, MXene is used as a substrate, and beta-FeOOH nano particles are grown on the surface of the MXene in situ, so that the exposure of active sites is greatly increased, and the conversion of the low-price Ti in the MXene into the low-price Fe (II) is promoted by the oxidation-reduction reaction between the low-price Ti (III) and the low-price Fe (III), so that the efficiency of heterogeneous Fenton reaction is improved, and the oxidation efficiency of nitrite is further improved.
3) The beta-FeOOH nano rod anchored on the MXene monomer greatly reduces the leaching of iron ions, and the leaching rate of the iron ions after 12 times of circulation is only 1.83%, which has important significance for reducing secondary pollution of water body;
4) The beta-FeOOH@MXene composite nanomaterial catalyst can be recycled, has good catalytic activity (more than 97 percent) after 12 times of circulation, can realize the resource utilization of nitrite economically and efficiently, and has a very wide application prospect.
5) The MXene has film forming property, and the surface and the edge of the MXene have rich functional groups such as hydroxyl, carboxyl and epoxy groups, so that the MXene film has good hydrophilicity and high porosity; in addition, the beta-FeOOH nano particles grow in situ in the MXene matrix to form a large number of beta-FeOOH@MXene hybrid functional units, so that the interlayer spacing of the MXene monomer is greatly increased, and the water flux is further improved. Therefore, the catalyst can form a film and is attached to the front of the evaporation crystallization area of the waste liquid at the tail part of the reaction tower, so that nitrite is efficiently oxidized and recrystallized.
Drawings
FIG. 1 is an XPS plot of the [email protected] obtained in example 1;
FIG. 2 is an XRD pattern of [email protected] obtained in example 1;
FIG. 3 is an SEM image of the [email protected] obtained in example 1;
FIG. 4 is an XRD pattern of MXene obtained in comparative example 1;
FIG. 5 is a TEM image of MXene obtained in comparative example 1;
FIG. 6 is Fe as a product obtained in comparative example 2 2 O 3 An XRD pattern of (b);
FIG. 7 is Fe as a product obtained in comparative example 2 2 O 3 SEM images of (a).
FIG. 8 is a conceptual diagram of an actual application of a β -FeOOH@MXene composite film
Detailed Description
The following examples are presented to illustrate the solutions described in this application. This solution is merely illustrative of the solution, so that it is understood that it is not limited to the application, which can be carried out in many different ways, as defined and covered by the claims.
Example 1
A catalyst for efficiently catalyzing and oxidizing nitrite (the mass ratio of beta-FeOOH to MXene is 1:0.2) is prepared by the following steps:
1) Preparation of MXene few layer dispersion: 2g of lithium fluoride was added to 40mL of 9mol/L hydrochloric acid, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Dissolving in the above solution under stirring (35deg.C, 24 h); after the pH of the supernatant is higher than 6 by ultrasonic centrifugation for a plurality of times, the supernatant is settledAdding 40mL of ethanol into the starch, and carrying out ultrasonic treatment for 1h (750W) to obtain an MXene few-layer nano-sheet; centrifuging the solution (3500-5000 r/min), and collecting a few-layer dispersion (2 mg/mL);
2) Preparation of 0.9M ferric chloride solution: weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark;
3) Weighing 4mL of the ferric chloride solution prepared in the step 2), dispersing in 30mL of the MXene few-layer dispersion prepared in the step 1), stirring, dispersing, and pouring into a reaction kettle for hydrothermal treatment (the hydrothermal temperature is 150 ℃ for 12 h); and centrifuging, washing and drying the product (50 ℃ for 4 hours) to obtain the [email protected] composite powder.
The analysis results of the chemical composition and chemical valence state of the elements in the composite material by using the X-ray photoelectron spectroscopy of the product obtained in the embodiment are shown in figure 1, and four characteristic peaks of C1 s (284.9 eV), O1 s (531 eV), fe 2p (711.5 eV) and Ti 2p (458.8 eV) of the beta-FeOOH@MXene composite nano material can be obviously observed in the figure. The product obtained in this example was analyzed by X-ray diffraction characterization, and as shown in fig. 2, diffraction peaks appear at 2θ=11.82 °, 26.73 °, 35.27 °, and 55.92, and the above diffraction peaks were found to correspond to the (110), (130), (211), and (251) crystal planes of β -FeOOH by contrast XRD card (pdf#75-1594). The product obtained in the embodiment utilizes a scanning electron microscope to perform morphological structure characterization on the composite material, and the synthesized beta-FeOOH@MXene composite nano material has a nano rod-shaped structure.
Example 2
A catalyst for efficiently catalyzing and oxidizing nitrite (the mass ratio of beta-FeOOH to MXene is 1:0.1) is prepared by the following steps:
1) Preparation of MXene few layer dispersion: 2g of lithium fluoride was added to 40mL of 9mol/L hydrochloric acid, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Dissolving in the above solution under stirring (35deg.C, 24 h); after the pH of the supernatant is higher than 6 by ultrasonic centrifugation for many times, adding 40mL of ethanol into the precipitate, and carrying out ultrasonic treatment for 1h (750W) to obtain an MXene few-layer nano-sheet; centrifuging the solution (3500-5000 r/min), and collecting a few-layer dispersion (2 mg/mL);
2) Preparation of 0.9M ferric chloride solution: weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark;
3) Measuring 2mL of the ferric chloride solution prepared in 2) and dispersing in 30mL of the MXene few-layer dispersion prepared in 1), stirring and dispersing, and pouring into a reaction kettle for hydrothermal treatment (the hydrothermal temperature is 150 ℃ for 12 h); and centrifuging, washing and drying the product (50 ℃ for 4 hours) to obtain the [email protected] composite powder.
Example 3
A catalyst for efficiently catalyzing and oxidizing nitrite (the mass ratio of beta-FeOOH to MXene is 1:0.3) is prepared by the following steps:
1) Preparation of MXene few layer dispersion: 2g of lithium fluoride was added to 40mL of 9mol/L hydrochloric acid, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Dissolving in the above solution under stirring (35deg.C, 24 h); after the pH of the supernatant is higher than 6 by ultrasonic centrifugation for many times, adding 40mL of ethanol into the precipitate, and carrying out ultrasonic treatment for 1h (750W) to obtain an MXene few-layer nano-sheet; centrifuging the solution (3500-5000 r/min), and collecting a few-layer dispersion (2 mg/mL);
2) Preparation of 0.9M ferric chloride solution: weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark;
3) Weighing 6mL of the ferric chloride solution prepared in 2) and dispersing in 30mL of the MXene few-layer dispersion prepared in 1), stirring and dispersing, and pouring into a reaction kettle for hydrothermal treatment (the hydrothermal temperature is 150 ℃ for 12 h); and centrifuging, washing and drying the product (at 50 ℃ for 12 hours) to obtain the [email protected] composite powder.
Comparative example 1
A few layer MXene dispersion was prepared as follows:
1) 2g of lithium fluoride was added to 40mL of 9mol/L hydrochloric acid, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Dissolving in the above solution under stirring (35deg.C, 24 h); after the pH of the supernatant is higher than 6 by ultrasonic centrifugation for many times, adding 40mL of ethanol into the precipitate, and carrying out ultrasonic treatment for 1h (750W) to obtain an MXene few-layer nano-sheet; will beCentrifuging the solution (3500-5000 r/min), and collecting a few-layer dispersion liquid (2 mg/mL);
2) The product obtained in the comparative example is subjected to X-ray diffraction characterization, and the result is shown in fig. 4, wherein a characteristic peak appears near 2θ=6.57 DEG, belongs to a (002) crystal face, and proves the formation of MXene; the results of transmission electron microscopy characterization of the products are shown in FIG. 5, from which the MXene lamellar structure can be observed.
Comparative example 2
Fe 2 O 3 Particles, the preparation method of which is as follows:
1) Weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark to obtain a ferric chloride solution with the concentration of 0.9M; weighing 20mL of ferric chloride solution, placing into a reaction kettle, performing hydrothermal treatment at 150 ℃ for 12 hours, centrifuging and washing for multiple times, and then placing into a drying oven for drying (at 50 ℃ for 12 hours) to obtain reddish brown Fe 2 O 3 And (3) powder.
2) The product of this comparative example was characterized by X-ray diffraction and the results are shown in FIG. 6, which shows that FeCl is present in the absence of MXene 3 Fe which directly forms crystalline phase after hydrothermal treatment 2 O 3 The XRD cards (PDF # 87-1165) were compared with the diffraction peaks evident near 2θ=24.34°, 33.44 °, 35.89 °, 41.08 °, 49.61 °, 54.24 °, and the above characteristic peaks were found to correspond to (012), (104), (110), (113), (024), and (116) crystal planes, respectively. The product obtained in this comparative example was subjected to scanning electron microscope characterization, the results are shown in FIG. 7, and Fe is shown in the figure 2 O 3 The particles exist in the form of irregular spindles of large diameter (about 4-5 μm).
Application example
The beta-FeOOH@MXene composite nanomaterial obtained in example 1 is applied to a catalytic oxidation sodium nitrite experiment, and specifically comprises the following steps:
experimental conditions: 0.2g NaNO 2 Dissolving in 200mL deionized water, adding 14.4mM H after complete dissolution 2 O 2 And (3) regulating the pH of the solution to 7, and then adding 0.05g of beta-FeOOH@MXene composite nanomaterial catalyst. After stirring for 30min, the solution was tested according to GB 7493-87In the method for preparing the nitrite in the solution, 0.02mL of solution to be detected is taken, 2mL of 4g/L of sulfanilic acid solution is added, after standing for 3-5 min, 1mL of 2g/L of naphthalene ethylenediamine hydrochloride solution is added, the volume is fixed to 100mL, the solution is uniformly mixed, standing for 15min, the absorbance at the wavelength of 538nm is measured by a spectrophotometer, thus the nitrite concentration in the solution is calculated, and the oxidation efficiency is calculated according to the residual concentration of the nitrite after reaction and the nitrite concentration in the original solution.
Table 1 is a comparative table of catalytic efficiencies of the catalytic oxidation of sodium nitrite obtained in examples 1 to 3 and comparative examples 1 to 2
| Project | Catalytic efficiency |
| H 2 O 2 /β[email protected] | 99.47％ |
| H 2 O 2 /β[email protected] | 89.86％ |
| H 2 O 2 /β[email protected] | 93.20％ |
| H 2 O 2 /MXene | 54.07％ |
| H 2 O 2 /Fe 2 O 3 | 41.60％ |
| H 2 O 2 | 32.95％ |
As can be seen from Table 1, after the [email protected] nanocomposite catalyst is added, the catalytic oxidation efficiency reaches 99.47%, and compared with the MXene, the catalyst has a small layer (prepared in comparative example 1) and pure Fe 2 O 3 The oxidation rate of the particles (prepared in comparative example 2) without catalyst is respectively improved by 57.87%, 45.40% and 66.52%, and the catalytic oxidation efficiency is obviously improved. With MXene and pure Fe 2 O 3 Compared with the beta-FeOOH@MXene composite nano material, the beta-FeOOH@MXene composite nano material can induce a faster and more effective heterogeneous Fenton reaction, so that the introduced MXene can induce the formation of beta-FeOOH, and can generate HO with higher efficiency so as to promote the oxidation of sodium nitrite.
In practical production, the use of a powdery catalyst is disadvantageous in terms of product collection and catalyst recovery and reuse, resulting in a high cost investment. Compared with a powdery catalyst, the membrane process has the advantages of energy conservation, simple operation, less secondary environmental pollution, easy recovery and the like, and is an efficient wastewater treatment method. The MXene in the catalyst has film forming property. The MXene surface has rich functional groups, and hybridization between the MXene surface and beta-FeOOH also greatly increases interlayer spacing, so that the formed film has good hydrophilicity and high porosity, and larger water flux is ensured. For UV-heat/H 2 O 2 Comprehensive method of oxidation combined with dual-zone absorption to cooperatively remove SO 2 And NOx, the absorption liquid of the reaction tower is catalyzed and oxidized by the beta-FeOOH@MXene composite film and then enters an evaporation crystallization area, and the conceptual diagram is shown in figure 8, so that the purity of nitrate in the evaporation crystallization area can be ensured, and the catalyst film can be conveniently recycled. Has very wide application prospect.
The above is merely an example of the present method and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention also fall within the scope of the present invention, and the scope of the present invention should be defined by the claims and should be included in the scope of the present invention.
Claims (4)
1. The application of the beta-FeOOH@MXene nanocomposite catalyst in the catalytic oxidation of sodium nitrite is characterized in that: the beta-FeOOH@MXene nanocomposite is of a nanorod structure; the mass ratio of the beta-FeOOH to the MXene in the beta-FeOOH@MXene nanocomposite is 1:0.2;
the preparation method of the beta-FeOOH@MXene nanocomposite comprises the following steps:
1) Preparation of MXene few layer dispersion: 2g of lithium fluoride was added to 40mL of 9mol/L hydrochloric acid, and after complete dissolution, 2g of Ti was slowly added 3 AlC 2 Stirring the mixture in the solution for 24 hours; after the pH of the supernatant is higher than 6 through ultrasonic centrifugation for many times, adding 40mL of ethanol into the precipitate, and carrying out ultrasonic treatment for 1h to obtain an MXene few-layer nano-sheet; centrifuging the solution, and collecting a few-layer dispersion liquid, wherein the concentration of the few-layer dispersion liquid is 2mg/mL;
2) Preparation of 0.9M ferric chloride solution: weighing 61.43g of ferric chloride hexahydrate, adding water, stirring to dissolve the ferric chloride hexahydrate, transferring the ferric chloride into a 250mL volumetric flask, adding 1.2mL of concentrated hydrochloric acid, and fixing the volume to a scale mark;
3) Weighing 4mL of the ferric chloride solution prepared in the step 2), dispersing in 30mL of the MXene few-layer dispersion liquid prepared in the step 1), stirring, dispersing, and pouring into a reaction kettle for hydrothermal treatment; and centrifuging, washing and drying the product to obtain the beta-FeOOH@MXene composite powder.
2. The use according to claim 1, wherein in step 1) the stirring temperature is 30-35 ℃ and the stirring speed is 450r/min.
3. The use according to claim 1, wherein the ultrasonic power in step 1) is 750W and the centrifugal speed is 3500-5000 r/min.
4. The use according to claim 1, wherein the hydrothermal temperature in step 3) is 150 ℃ and the hydrothermal time is 12 hours.
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