CN113559903A - Sandwich-shaped Co3O4@ Mxenes composite material and preparation method and application thereof - Google Patents
Sandwich-shaped Co3O4@ Mxenes composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 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 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 89
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 18
- 231100000719 pollutant Toxicity 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000001994 activation Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- 229910021281 Co3O4In Inorganic materials 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000002386 leaching Methods 0.000 abstract description 8
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZBQKPDHUDKSCRS-UHFFFAOYSA-N $l^{1}-oxidanyl acetate Chemical compound CC(=O)O[O] ZBQKPDHUDKSCRS-UHFFFAOYSA-N 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 206010042772 syncope Diseases 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a sandwich-shaped Co3O4@ Mxenes composite material, preparation method thereof and application method for removing 2, 4-dichlorophenol in water by adopting @ Mxenes composite material to activate peroxyacetic acid3AlC2Immersing in HF, sealing in a polytetrafluoroethylene cup, and heating to obtain Ti3C2TXThen with Co (NO)3)2·6H2Obtaining sandwich-shaped Co after O mixing reaction3O4@ Mxenes composites. The sandwich Co provided by the invention3O4The @ Mxenes composite material activates peracetic acid to generate organic free radical, oxidizes and degrades 2, 4-dichlorophenol in water body, compared with other materialsActivation method ═ Co3O4The @ Mxenes composite material can efficiently activate peroxyacetic acid with a unique sandwich structure, has low leaching rate of metal cobalt ions, solves the problem of secondary pollution to the environment caused by leaching of the metal ions, and is an environment-friendly catalyst.
Description
Technical Field
The invention relates to the technical field of water pollution control, in particular to a sandwich-shaped Co3O4@ Mxenes composite material, a preparation method thereof and an application method for removing 2, 4-dichlorophenol in water by using activated peroxyacetic acid.
Background
2, 4-dichlorophenol (2,4-DCP) is generated from chlorophenol pollutants in a priority pollutant list of China in a plurality of industries such as coking, printing and dyeing, plastics, oil refining and the like, has strong toxicity and odor, can cause anemia, syncope, acne and pruritus, and even can cause cancer. Although the concentration of the natural water is low, the potential threat to human health and ecological environment caused by the natural water is not ignored, and the natural water becomes a pollutant concerned by people. 2, 4-dichlorophenol (2,4-DCP) is a common chlorophenol pollutant, has poor biodegradability, is difficult to degrade by the traditional process, and has high treatment difficulty. Therefore, there is a need to develop an environmentally friendly, efficient and economical treatment method.
In recent years, advanced oxidation technology is considered as one of the most promising technologies for degrading different kinds of organic compounds, microorganisms and emerging pollutants, which oxidize organic pollutants by radicals generated by an oxidizing agent. Peroxyacetic acid is a strong oxidant with a very high standard reduction potential (E)01.96V), close to H2O2Higher than chlorine or chlorine dioxide. The thermal stability of the polymer is mainly determined by the dissociation energy of O-O bonds, and the ratio of O-O bonds (159kJ/mol) to H of the peroxyacetic acid2O2(213kJ/mol) weak, the peracetic acid solution can decompose naturally at room temperature. Compared with other oxidation technologies, peroxyacetic acid based advanced oxidation technologies have the advantages of strong oxidation capacity, low pH dependence, less generation of toxic byproducts in treated wastewater and the like, so that the peroxyacetic acid has more and more attention on the aspects of inactivating pathogens in wastewater and removing newly-appeared difficultly-degradable pollutants. Peroxyacetic acid is required to generate active free radicals to degrade pollutants through an activation process, and the activation of the peroxyacetic acid is reportedMethods including UV irradiation and addition of transition metal ions indicate that these activation methods have great potential for contaminant treatment. However, ultraviolet irradiation has limited permeability to water and cannot be applied to treatment of groundwater. Compared with other metals, the transition metals (Co, Fe, Cu and Mn) have the advantages of low cost and reusability. Wherein Co2+the/PMS system shows the best performance at neutral pH and lower reagent dosage, even better than the traditional Fenton reaction. However, leaching of metallic cobalt may lead to metal contamination and ecotoxicity. Therefore, relatively high stability of Co-based3O4Have been widely studied.
MXenes are two-dimensional materials composed of transition metal carbides, carbonitrides or nitrides. Such two-dimensional materials have Mn+1XnGeneral formula (II) is shown. In the formula, the letter M represents a transition metal (Ti, Mo, V, Ta, Nb, Cr, etc.), and the letter X represents C or N. MXenes have many functional groups on their surface. In this regard, the general formula for MXenes can be generalized to Mn+1XnTxWherein T represents a surface termination (e.g., -O, -F, or-OH). As more and more two-dimensional materials are discovered, the discovery of MXenes has gained wide acceptance and has milestone significance. The structure and excellent performance of MXenes make it widely used in the fields of batteries, capacitors, catalysis, electromagnetic shielding, absorption, etc. Ti3C2TxIs the first MXenes, and is also the most commonly used type of MXenes. It is obtained by selective etching of Ti3AlC2Phase metal aluminum layer. The unique layered structure of MXenes provides a larger space for the immobilization of the functional nano-materials, improves the distribution of the functional nano-materials on the surface of MXenes, and provides a possible application prospect for the MXenes as a potential support material for environmental remediation (such as catalysis and adsorption). However, little is known about its possible use in water purification. It is reported that Fe3O4the/MXenes composite material has excellent removal performance on phosphate in wastewater. In a word, MXenes has rich active centers and high specific surface area in the aspect of pollutant removal, has wide application prospect and belongs to the field of environmental remediation of advanced oxidation technologyThe popularization and the application of the method provide opportunities.
Here we use for the first time sandwich Co3O4The @ Mxenes compound is used as a heterogeneous catalyst to activate peracetic acid to remove 2, 4-dichlorophenol in water. In this system the acetylperoxy radical CH3C (═ O) OO · proved to be the main active component of the reaction, Mxenes material accelerated Co3O4Surface ≡ Co2+-≡Co3+-≡Co2+(see equations 1 and 2), thereby significantly strengthening Co3O4Activating effect on peroxyacetic acid. The leaching condition of the cobalt ions in the system is further researched, and the leaching amount of the cobalt ions after reaction is only about 0.02mg/L and is far lower than the standard cobalt ion concentration limit value (1.0mg/L) of the surface water environment quality in China.
≡Co(II)+CH3CO3H→≡Co(III)+CH3CO2 ·+OH- (1)
≡Co(III)+CH3CO3H→≡Co(II)+CH3CO3 ·+H+ (2)
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a sandwich-shaped Co3O4@ Mxenes composite material, a preparation method thereof and an application method for removing 2, 4-dichlorophenol in water by using activated peroxyacetic acid. The invention mainly overcomes the technical problems that: the catalytic activity of the catalyst is not high, the stability of the catalyst is poor, and the leaching of metal ions influences the ecological environment and causes secondary pollution.
The technical scheme of the invention is as follows: sandwich-shaped Co3O4The preparation method of the @ Mxenes composite material comprises the following steps:
(1) mixing 3g of Ti3AlC2Immersing in 35mL of HF, sealing in a polytetrafluoroethylene cup, reacting at 313K, washing the obtained material with deionized water, centrifuging for 3-5 times to remove residual impurities, and drying in a vacuum oven at 333K overnight until constant weight is achieved to obtain Ti3C2TXWherein T represents surface terminationA terminal end, the surface termination comprising-O, -F, or-OH;
(2) ti obtained in the step (1)3C2TXAnd 0.35g to 1.05g of Co (NO)3)2·6H2Mixing O into deionized water, and violently stirring the mixture to evaporate water at the rotating speed of 400-500 rpm;
(3) grinding the obtained product into powder, heating to 473K at room temperature, and reacting for 12 h; cooling to room temperature, washing with deionized water for three times to remove residual impurities to obtain sandwich-shaped Co3O4@ Mxenes composites.
Further, Co (NO) in the step (2)3)2·6H2The amount of O added was 0.7 g.
Further, Co attached in the composite material3O4The grain diameter is 25 nm-50 nm.
The invention also provides the sandwich Co3O4The application method of the @ Mxenes composite material for activating peracetic acid to remove 2, 4-dichlorophenol in water comprises the following steps: adding peroxyacetic acid and the sandwich Co as catalyst into the sewage containing 2, 4-dichlorophenol as organic pollutant3O4@ Mxenes composites; adding peroxyacetic acid and the sandwich Co3O4In a mixed solution of @ Mxenes composite material, the sandwich-shaped Co3O4The concentration of the @ Mxenes composite material is 5 mg/L-50 mg/L, the concentration of the peroxyacetic acid is 0.05 mM-1.04 mM, and after the reaction is carried out for 2 min-20 min at normal temperature, the pollutant 2, 4-dichlorophenol in the sewage is removed.
Further, the concentration of the oxidant peracetic acid in the catalytic system was 0.26 mM.
Further, the concentration of the catalyst in the catalyst system is 10 mg/L.
Further, the concentration of the target contaminant 2, 4-dichlorophenol was 20. mu.M.
Further, the reaction was carried out at an initial pH of 7.0.
Further, the reaction time was 20 min.
Further, the sandwich-shaped Co3O4The @ Mxenes composite material is repeatedly recycled for 4 times, and the pollutant removal rate can still reach over 90 percent; the catalyst is recovered by filtration and then dried, and can be reused without additional activation.
The invention has the following beneficial technical effects:
mixing the obtained sandwich-shaped Co3O4The @ Mxenes composite material is in a sandwich shape, and Co3O4Nanoparticles are adhered to the surface and interlayer of MXene, Mxene and Co3O4Stable bonding between nanoparticles, Co3O4The particles can be uniformly dispersed, and thus the catalytic activity is high. Co3O4@ Mxenes can effectively activate peroxyacetic acid over a wide pH range, covering most wastewater pH ranges. Sandwich-shaped Co prepared by adopting preparation method of application3O4The @ Mxenes composite material is used as a heterogeneous catalyst, and has good stability and reusability due to the unique morphology structure. Researches show that the sandwich-shaped Co prepared by the preparation method of the application3O4When the @ Mxenes composite material is used as a heterogeneous catalyst to activate peroxyacetic acid to remove 2, 4-dichlorophenol in water, the leaching rate of metal cobalt ions is very low, the problem of secondary pollution to the environment caused by leaching of the metal ions is solved, and the catalyst is an environment-friendly catalyst. The invention uses self-prepared sandwich-shaped Co for the first time3O4The method for activating peroxyacetic acid by the @ Mxenes composite material has a good effect of removing 2, 4-dichlorophenol in water, and after the reaction is carried out for 20min, the removal rate of the 2, 4-dichlorophenol reaches about 98%, so that the research of the activated peroxyacetic acid in the field of sewage treatment is promoted.
Drawings
FIG. 1 shows a sandwich-shaped Co prepared by the preparation method of the present invention3O4Electron microscopy of @ mxexens composites;
FIG. 2 is a schematic representation of the effect of initial pH on the degradation of 2, 4-dichlorophenol in application example 1 of the present invention;
FIG. 3 shows an embodiment of the present invention2 different sandwich Co3O4The schematic diagram of the influence of the added amount of the @ Mxenes composite material on the degradation of 2, 4-dichlorophenol after the peroxyacetic acid is activated;
FIG. 4 shows an application example 3 of the present invention using a sandwich Co3O4Schematic representation of the effect of different concentrations of peroxyacetic acid activated by @ mxexes composite on the degradation of 2, 4-dichlorophenol.
Detailed Description
The present invention will next be described in detail with reference to examples. However, the examples listed below do not limit the scope of the present invention.
Example 1
(1) Mixing 3g of Ti3AlC2Immersing in 35mL of HF, sealing in a polytetrafluoroethylene cup, reacting at 313K, washing the obtained material with deionized water, centrifuging for 3-5 times to remove residual impurities, and drying in a vacuum oven at 333K overnight until constant weight is achieved to obtain Ti3C2TXAnd T represents a surface termination (e.g., -O, -F, or-OH).
(2) Mixing Ti3C2TXAnd 0.35g of Co (NO)3)2·6H2And O is mixed into deionized water, and the mixture is stirred vigorously to evaporate water, wherein the rotating speed is 400-500 rpm.
(3) Grinding the obtained product into powder, heating to 473K at room temperature at the heating rate of 2K/min, and reacting for 12 h. After cooling to room temperature, it was washed three times with deionized water to remove residual impurities, yielding Co as shown in FIG. 13O4@ Mxenes composite, labeled CM-10%.
Example 2
(1) Mixing 3g of Ti3AlC2Immersing in 35mL of HF, sealing in a polytetrafluoroethylene cup, reacting at 313K, washing the obtained material with deionized water, centrifuging for 3-5 times to remove residual impurities, and drying in a vacuum oven at 333K overnight until constant weight is achieved to obtain Ti3C2TXAnd T represents a surface termination (e.g., -O, -F, or-OH).
(2) Mixing Ti3C2TXAnd 0.7g of Co (NO)3)2·6H2And O is mixed into deionized water, and the mixture is stirred vigorously to evaporate water, wherein the rotating speed is 400-500 rpm.
(3) Grinding the obtained product into powder, heating to 473K at room temperature at the heating rate of 2K/min, and reacting for 12 h. Cooling to room temperature, washing with deionized water for three times to remove residual impurities to obtain Co3O4@ Mxenes composite, labeled CM-20%.
Example 3
(1) Mixing 3g of Ti3AlC2Immersing in 35mLHF, sealing in a polytetrafluoroethylene cup, reacting at 313K, washing the obtained material with deionized water, centrifuging for 3-5 times to remove residual impurities, and drying in a vacuum oven at 333K overnight until constant weight is reached to obtain Ti3C2TXAnd T represents a surface termination (e.g., -O, -F, or-OH).
(2) Mixing Ti3C2TXAnd 1.05g of Co (NO)3)2·6H2And O is mixed into deionized water, and the mixture is stirred vigorously to evaporate water, wherein the rotating speed is 400-500 rpm.
(3) Grinding the obtained product into powder, heating to 473K at room temperature at the heating rate of 2K/min, and reacting for 12 h. Cooling to room temperature, washing with deionized water for three times to remove residual impurities to obtain Co3O4@ Mxenes composite, labeled CM-30%.
Application example 1
To the prepared aqueous solution containing 2, 4-dichlorophenol and peracetic acid, a catalyst (CM-20%) was added, and experiments were performed at initial pH values of 4, 5, 6, 7, 8, and 9, respectively. Adding peroxyacetic acid and the sandwich Co3O4The mixed solution of @ Mxenes composite material contains peroxyacetic acid as oxidant 0.26mM and catalyst (Co)3O4@ Mxenes) was added in an amount of 10mg/L, the concentration of the target contaminant 2, 4-dichlorophenol was 20. mu.M, and the reaction time was 20 min. The concentration of 2, 4-dichlorophenol was measured by sampling at predetermined times (0min, 2min, 5min, 10min, 15min, 20 min). 2(C) for removing 4-dichlorophenolt/C0) Is represented by C0Is the initial concentration of 2, 4-dichlorophenol, CtThe concentration of 2, 4-dichlorophenol at time t. As shown in figure 1, the treatment effect is best when the pH value is 7, and the removal rate of the pollutant 2, 4-dichlorophenol after 20min treatment reaches about 98%.
Application example 2
To the prepared aqueous solution containing 2, 4-dichlorophenol and peracetic acid, a catalyst (CM-20%) was added, and experiments were carried out at catalyst (CM-20%) addition levels of 5mg/L, 10mg/L, 20mg/L, 30mg/L, and 50mg/L, respectively. Initial pH 7, adding peracetic acid and the sandwich Co3O4In the mixed solution of the @ Mxenes composite material, the concentration of an oxidant peracetic acid is 0.26mM, the concentration of a target pollutant 2, 4-dichlorophenol is 20 mu M, and the reaction time is 20 min. The concentration of 2, 4-dichlorophenol was measured by sampling at predetermined times (0min, 2min, 5min, 10min, 15min, 20 min). (C) for removing 2, 4-dichlorophenolt/C0) Is represented by C0Is the initial concentration of 2, 4-dichlorophenol, CtThe concentration of 2, 4-dichlorophenol at time t. As shown in fig. 2, the removal efficiency of 2, 4-dichlorophenol increased with increasing catalyst addition in the range of catalyst (CM-20%) for this experimental design. When the addition amount of the catalyst (CM-20%) is 50mg/L, the treatment effect is optimal, and the removal rate of the pollutant 2, 4-dichlorophenol after 9min treatment reaches about 98%.
Application example 3
To the prepared aqueous solution containing 2, 4-dichlorophenol and peracetic acid was added a catalyst (CM-20%), and experiments were conducted at concentrations of the oxidants peracetic acid of 0.05mM, 0.10mM, 0.26mM, 0.52mM, 1.04mM, respectively. Initial pH 7, adding peracetic acid and the sandwich Co3O4In the mixed solution of the @ Mxenes composite material, the addition amount of a catalyst (CM-20%) is 10mg/L, the concentration of a target pollutant 2, 4-dichlorophenol is 20 mu M, and the reaction time is 20 min. The concentration of 2, 4-dichlorophenol was measured by sampling at predetermined times (0min, 2min, 5min, 10min, 15min, 20 min). (C) for removing 2, 4-dichlorophenolt/C0) Is represented by C0Is the initial concentration of 2, 4-dichlorophenol, CtThe concentration of 2, 4-dichlorophenol at time t. As shown in figure 3, the treatment effect is best when the concentration of the peroxyacetic acid oxidant is 0.26mM, and the removal rate of the pollutant 2, 4-dichlorophenol after 20min treatment reaches about 98%.
Claims (10)
1. Sandwich-shaped Co3O4The preparation method of the @ Mxenes composite material is characterized by comprising the following steps of:
(1) mixing 3g of Ti3AlC2Immersing in 35mL of HF, sealing in a polytetrafluoroethylene cup, reacting at 313K, washing the obtained material with deionized water, centrifuging for 3-5 times to remove residual impurities, and drying in a vacuum oven at 333K overnight until constant weight is achieved to obtain Ti3C2TXWherein T represents a surface termination comprising-O, -F, or-OH;
(2) ti obtained in the step (1)3C2TXAnd 0.35g to 1.05g of Co (NO)3)2·6H2Mixing O into deionized water, and violently stirring the mixture to evaporate water at the rotating speed of 400-500 rpm;
(3) grinding the obtained product into powder, heating to 473K at room temperature, and reacting for 12 h; cooling to room temperature, washing with deionized water for three times to remove residual impurities to obtain sandwich-shaped Co3O4@ Mxenes composites.
2. Co produced by the production method according to claim 13O4@ Mxenes composite material characterized in that Co (NO) in said step (2)3)2·6H2The amount of O added was 0.7 g.
3. Co produced by the production method according to claim 13O4@ Mxenes composite material characterized by Co attached in said composite material3O4The grain diameter is 25 nm-50 nm.
4. Using a sandwich-type Co according to claim 23O4The method for removing 2, 4-dichlorophenol in water by activating peracetic acid by the @ Mxenes composite material is characterized by comprising the following steps: adding peroxyacetic acid and the sandwich Co as catalyst into the sewage containing 2, 4-dichlorophenol as organic pollutant3O4@ Mxenes composites; adding peroxyacetic acid and the sandwich Co3O4In a mixed solution of @ Mxenes composite material, the sandwich-shaped Co3O4The concentration of the @ Mxenes composite material is 5 mg/L-50 mg/L, the concentration of the peroxyacetic acid is 0.05 mM-1.04 mM, and after the reaction is carried out for 2 min-20 min at normal temperature, the pollutant 2, 4-dichlorophenol in the sewage is removed.
5. Sandwich-shaped Co according to claim 43O4The application method of the @ Mxenes composite material for activating peroxyacetic acid to remove 2, 4-dichlorophenol in water is characterized in that the concentration of the peroxyacetic acid serving as an oxidant in a catalytic system is 0.26 mM.
6. Sandwich-shaped Co according to claim 43O4The application method of the @ Mxenes composite material for activating peroxyacetic acid to remove 2, 4-dichlorophenol in water is characterized in that the concentration of a catalyst in a catalytic system is 10 mg/L.
7. Sandwich-shaped Co according to claim 43O4The application method of the @ Mxenes composite material for activating peracetic acid to remove 2, 4-dichlorophenol in water is characterized in that the concentration of the target pollutant 2, 4-dichlorophenol is 20 mu M.
8. Sandwich-shaped Co according to claim 43O4Application method of @ Mxenes composite material for activating peroxyacetic acid to remove 2, 4-dichlorophenol in water, which is characterized in that the reaction is carried out at an initial pH of 7.0.
9. Sandwich-shaped Co according to claim 43O4The application method of the @ Mxenes composite material for activating peroxyacetic acid to remove 2, 4-dichlorophenol in water is characterized in that the reaction time is 20 min.
10. Sandwich-shaped Co according to claim 43O4The application method of @ Mxenes composite material for removing 2, 4-dichlorophenol in water by activating peroxyacetic acid is characterized in that the sandwich-shaped Co composite material3O4The @ Mxenes composite material is repeatedly recycled for 4 times, and the pollutant removal rate can still reach over 90 percent; the catalyst is recovered by filtration and then dried, and can be reused without additional activation.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114870882A (en) * | 2022-06-13 | 2022-08-09 | 齐齐哈尔大学 | Catalyst for quickly activating peroxyacetic acid to oxidize and degrade antibiotic wastewater based on microwaves and preparation and application methods thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105854882A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Magnetic Co3O4-C nano material and preparation method thereof as well as application of magnetic Co3O4-C nano material as catalyst for activating peroxymonosulfate to wastewater treatment |
CN106971854A (en) * | 2017-04-18 | 2017-07-21 | 西安交通大学 | The two-dimensional layer Ti of transition metal oxide nano particle doping3C2Film nano composite material and preparation method thereof |
CN109941997A (en) * | 2019-03-29 | 2019-06-28 | 陕西科技大学 | A kind of hemoglobin shape Co3O4/Ti3C2The preparation method and application of nanocomposite |
US20200254396A1 (en) * | 2020-04-03 | 2020-08-13 | Qatar University | Precise Fabrication of Activated-Hydrophilic-Hydrophobic MXenes-based Multidimensional Nanosystems for Efficient and Prompt Water Purification from Petroleum Wastes and Desalination Process under Ambient Conditions |
CN111799095A (en) * | 2020-06-15 | 2020-10-20 | 桂林电子科技大学 | Hollow MXenes-based metal oxide composite material and preparation method and application thereof |
WO2021113509A1 (en) * | 2019-12-03 | 2021-06-10 | Drexel University | Dispersion and stabilization of mxene materials and mxene materials for energy storage applications |
-
2021
- 2021-06-24 CN CN202110701911.7A patent/CN113559903A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105854882A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Magnetic Co3O4-C nano material and preparation method thereof as well as application of magnetic Co3O4-C nano material as catalyst for activating peroxymonosulfate to wastewater treatment |
CN106971854A (en) * | 2017-04-18 | 2017-07-21 | 西安交通大学 | The two-dimensional layer Ti of transition metal oxide nano particle doping3C2Film nano composite material and preparation method thereof |
CN109941997A (en) * | 2019-03-29 | 2019-06-28 | 陕西科技大学 | A kind of hemoglobin shape Co3O4/Ti3C2The preparation method and application of nanocomposite |
WO2021113509A1 (en) * | 2019-12-03 | 2021-06-10 | Drexel University | Dispersion and stabilization of mxene materials and mxene materials for energy storage applications |
US20200254396A1 (en) * | 2020-04-03 | 2020-08-13 | Qatar University | Precise Fabrication of Activated-Hydrophilic-Hydrophobic MXenes-based Multidimensional Nanosystems for Efficient and Prompt Water Purification from Petroleum Wastes and Desalination Process under Ambient Conditions |
CN111799095A (en) * | 2020-06-15 | 2020-10-20 | 桂林电子科技大学 | Hollow MXenes-based metal oxide composite material and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
WEI WU等: "Degradation of organic compounds by peracetic acid activated with Co3O4: A novel advanced oxidation process and organic radical contribution", 《CHEMICAL ENGINEERING JOURNAL》 * |
YUXIN LIU等: "Sandwich-like Co3O4/MXene composite with enhanced catalytic performance for Bisphenol A degradation", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114870882A (en) * | 2022-06-13 | 2022-08-09 | 齐齐哈尔大学 | Catalyst for quickly activating peroxyacetic acid to oxidize and degrade antibiotic wastewater based on microwaves and preparation and application methods thereof |
CN114870882B (en) * | 2022-06-13 | 2023-06-23 | 齐齐哈尔大学 | Catalyst for oxidizing and degrading antibiotic wastewater based on microwave rapid activation of peroxyacetic acid and preparation and application methods thereof |
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