CN115845903A - Based on CoFe 2 O 4 @ CN AOP high-efficiency catalyst and preparation method thereof - Google Patents
Based on CoFe 2 O 4 @ CN AOP high-efficiency catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910003321 CoFe Inorganic materials 0.000 title claims abstract 13
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- 229940011182 cobalt acetate Drugs 0.000 claims description 24
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 24
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 24
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims 7
- 239000000956 alloy Substances 0.000 claims 7
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 18
- 238000004806 packaging method and process Methods 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000012425 OXONE® Substances 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method based on CoFe 2 O 4 The invention discloses a @ CN AOP high-efficiency catalyst and a preparation method thereof, belongs to the field of advanced oxidation catalysis of heterogeneous catalysts, and relates to a method for in-situ construction of CoFe with coordinated unsaturated sites through acetic acid hydrolysis 2 O 4 @ CN, the coordination unsaturated site center is constructed by means of acetate coordination, the dispersion degree of Co and Fe atoms is improved by CN loading, and meanwhile, a large number of coordination unsaturated active catalytic centers are introduced, so that the catalytic efficiency is improved. The Co and Fe bimetallic coordination unsaturated active center provided by the invention can be used for carrying out rapid and continuous catalytic oxidation by respectively taking Co and Fe as the active centers, so as to realize rapid degradation of methylene blue.
Description
Technical Field
The invention belongs to the field of advanced oxidation catalysis of heterogeneous catalysts, and relates to a catalyst based on CoFe 2 O 4 @ CN AOP high-efficiency catalyst and a preparation method thereof.
Background
Methylene blue belongs to typical organic dye wastewater difficult to degrade, is one of the most harmful industrial wastewater, and the treatment problem of the methylene blue is one of the difficulties in the environmental field. Advanced oxidation technologies (AOPs) are a very effective method for treating difficult-to-treat organic pollutants, and advanced oxidation technologies based on sulfate radicals (. SO 4-) have been developed as an emerging advanced oxidation technology. The activation of potassium peroxymonosulfate and potassium peroxydisulfate is the main way to generate sulfate radical, and some of the most common activation methods in the prior art need additional energy, some have high treatment cost, and some can generate secondary pollution. Therefore, it is necessary to explore a method for activating potassium persulfate salt with simple operation, high efficiency and safety.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a CoFe-based material 2 O 4 An AOP high-efficiency catalyst of @ CN and a preparation method thereof, aiming at solving the problem of CoFe in the prior art 2 O 4 Particle agglomeration and low reaction catalysis efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
based on CoFe 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst comprises the following steps:
s1: mixing and stirring DMF and absolute ethyl alcohol to prepare a solvent A;
s2: dissolving iron acetate and cobalt acetate in the solvent A, and stirring until the iron acetate and the cobalt acetate are completely dissolved to prepare a solution B;
s3: dissolving 2-amino terephthalic acid in the solution B, and stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C;
s4: carrying out hydrothermal reaction on the solution C, washing and drying to obtain a powder sample D;
s5: the powder sample D was vacuum dried and calcined in air atmosphereFiring to obtain a material based on CoFe 2 O 4 @ CN AOP high efficiency catalyst.
Preferably, in S1, DMF and absolute ethanol are mixed according to a ratio of 4:1 to 1:4 by volume.
Preferably, in the S2, iron acetate with the molar mass of 0.6-2 mmol and cobalt acetate with the molar mass of 0.3-1 mmol are dissolved in 20mL of the solvent A and stirred until the iron acetate and the cobalt acetate are completely dissolved to prepare a solution B.
Preferably, in the S3, 0.9-3 mmol of 2-amino terephthalic acid is dissolved in 20mL of the solution B and stirred until the solution B is completely dissolved to prepare a solution C.
Preferably, in the step S4, the solution C is poured into a polytetrafluoroethylene lining, and is packaged by a stainless steel hot pot for hydrothermal reaction, wherein the reaction temperature of the hydrothermal reaction is 150-180 ℃, and the reaction time is 18-24 hours.
Preferably, in S4, after the hydrothermal reaction is completed, washing with ethanol and deionized water, centrifuging each for 2 to 3 times, and drying to obtain a powder sample D.
Preferably, in S5, the powder sample D is placed in a vacuum drying oven at a vacuum degree of 10 -3 Pa, 100-120 deg.C, vacuum drying for 8-12 h.
Preferably, in the S5, the calcination is carried out in an air atmosphere, the calcination temperature is 400-700 ℃, and the calcination time is 2-3 h.
The invention also discloses a method based on CoFe 2 O 4 The @ CN AOP high-efficiency catalyst is prepared by adopting any one of the preparation methods.
Compared with the prior art, the invention has the following beneficial effects:
cobalt ferrite (CoFe) 2 O 4 ) Is one of PMS heterogeneous activated solid catalysts. However, the reactivity is low, so that high CoFe is usually required for the catalytic activation process 2 O 4 Load amount. For this purpose, increasing CoFe is proposed 2 O 4 Two strategies for reactivity: (1) Increasing CoFe 2 O 4 Specific surface area of (2) encapsulation of CoFe with an electron transfer medium 2 O 4 And (3) increasing CoFe 2 O 4 Reactive siteAnd (4) point. Based on the above points, it is proposed to derive carbon nitrogen loaded CoFe with coordinately unsaturated bimetallic site center by MOF 2 O 4 The material and the interaction between the substrate and the active component can promote the dispersion of the active component, enhance the adhesive force of the impregnated transition metal and adjust the electronic structure of the active component, thereby promoting the electron transfer and improving the activity and the stability of the catalyst. The invention loads CoFe through C/N 2 O 4 Nanoparticles, prevention of CoFe 2 O 4 Agglomeration of nanoparticles, wherein coordinatively unsaturated sites may simultaneously provide more catalytic sites; the Co and Fe bimetallic coordination unsaturated active center provided by the invention can be used for carrying out rapid and continuous catalytic oxidation by respectively taking Co and Fe as the active centers, so as to realize rapid degradation of methylene blue.
Drawings
FIG. 1 is CoFe of the present invention 2 O 4 SEM picture of @ CN;
FIG. 2 shows CoFe of the present invention 2 O 4 The degradation curve for the catalytic degradation of MB @ CN.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the technical scheme provided by the invention is as follows: based on CoFe 2 O 4 The AOP high-efficiency catalyst of @ CN and the preparation method thereof comprise the following steps:
step 1: DMF and absolute ethanol were mixed according to 4:1 to 1:4, mixing and stirring to prepare a solvent A;
step 2: dissolving ferric acetate with the molar mass of 0.6-2 mmol and cobalt acetate with the molar mass of 0.3-1 mmol in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to prepare solution B;
and step 3: dissolving 0.9-3 mmol of 2-amino terephthalic acid in 20mL of solution B, stirring until the 2-amino terephthalic acid is completely dissolved to prepare solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction at 150-180 ℃ for 18-24 h, washing and centrifuging the solution C for 2-3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum of 10 -3 Pa, 100-120 ℃, vacuum drying for 8-12 h, calcining at 400-700 ℃ for 2-3 h in air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 1:
step 1: DMF and absolute ethanol were mixed according to 4:1 to prepare a solvent A;
step 2: dissolving 0.6mmol of ferric acetate and 0.3mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 0.9mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 18 hours at 170 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum of 10 -3 And (3) drying for 8 hours in vacuum at the temperature of Pa and 110 ℃, and calcining for 2 hours at the calcining temperature of 400 ℃ in an air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 2:
step 1: DMF with absolute ethanol as 1:1 to prepare a solvent A;
and 2, step: dissolving 1.2mmol of ferric acetate and 0.6mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 1.8mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 21 hours at 170 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum of 10 -3 And (3) drying the mixture for 10 hours in vacuum at the temperature of Pa and 110 ℃, and calcining the mixture for 2 hours at the calcining temperature of 600 ℃ in an air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 3:
step 1: DMF and absolute ethanol were mixed according to 1:4, mixing and stirring to obtain a solvent A;
step 2: dissolving iron acetate with the molar mass of 2mmol and cobalt acetate with the molar mass of 1mmol in 20mL of solvent A, and stirring until the iron acetate and the cobalt acetate are completely dissolved to prepare solution B;
and step 3: dissolving 3mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 24 hours at 170 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum level of 10 -3 And (3) drying under vacuum at the temperature of 110 ℃ under Pa for 12 hours, and calcining under an air atmosphere at the calcining temperature of 700 ℃ for 2 hours. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 4:
step 1: DMF and absolute ethanol were mixed according to 1:1 to prepare a solvent A;
step 2: dissolving 0.6mmol of ferric acetate and 0.3mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 0.9mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 20 hours at 160 ℃, washing and centrifuging the solution C for 2 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum level of 10 -3 And (3) drying the mixture for 8 hours in vacuum at the temperature of Pa and 120 ℃, and calcining the mixture for 2.5 hours at the calcining temperature of 500 ℃ in an air atmosphere. Obtaining a product based on CoFe 2 O 4 AOP high efficiency catalyst sample of @ CN.
Example 5:
step 1: DMF and absolute ethanol were mixed according to 3:1 to prepare a solvent A;
step 2: dissolving 1mmol of ferric acetate and 0.5mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 0.9mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 18 hours at 180 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum of 10 -3 Pa, at 100 ℃, vacuum drying for 8h, and calcining at 400 ℃ for 3h in an air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 6:
step 1: DMF and absolute ethanol were mixed according to 2:1 to prepare a solvent A;
step 2: dissolving 1mmol of ferric acetate and 1mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 1.5mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 22 hours at 150 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
the collected powder sample D was then placed in a vacuum oven at a vacuum level of 10 -3 Pa,100 ℃, vacuum drying for 10h, and calcining at 500 ℃ for 2h in air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
Example 7:
step 1: DMF with absolute ethanol as 1:3 to obtain a solvent A;
step 2: dissolving 0.6mmol of ferric acetate and 0.6mmol of cobalt acetate in 20mL of solvent A, and stirring until the ferric acetate and the cobalt acetate are completely dissolved to obtain solution B;
and step 3: dissolving 1mmol of 2-amino terephthalic acid in the solution B, stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C, pouring the solution C into a polytetrafluoroethylene lining, packaging the solution C by using a stainless steel hot kettle, carrying out hydrothermal reaction for 18h at 170 ℃, washing and centrifuging the solution C for 3 times by using ethanol and deionized water, and collecting a powder sample D after drying;
then will collectThe resulting powder sample D was placed in a vacuum oven at a vacuum of 10 -3 And (3) drying for 8 hours in vacuum at the temperature of Pa and 110 ℃, and calcining for 2 hours at the calcining temperature of 400 ℃ in an air atmosphere. Obtaining a product based on CoFe 2 O 4 @ CN sample of AOP high efficiency catalyst.
FIG. 1 is CoFe with coordinately unsaturated sites 2 O 4 @ CN AOP catalyst CoFe 2 O 4 SEM transmission photograph of @ CN, coFe can be seen 2 O 4 The nano particles are successfully loaded on the surface of the N-doped C, the density is low, and pores in the structure are favorable for the catalytic reaction.
For the above CoFe 2 O 4 The performance of @ CN in catalyzing PMS to degrade methylene blue was evaluated, and FIG. 2 shows that in CoFe 2 O 4 Under the action of @ CN, 99% of high-efficiency degradation can be completed on methylene blue within 40 minutes, which indicates that CoFe 2 O 4 @ CN has excellent catalytic properties.
In conclusion, the invention discloses CoFe with coordinately unsaturated sites 2 O 4 @ CN AOP catalyst and a preparation method thereof. The method comprises the step of in-situ construction of CoFe with coordination unsaturated sites through acetic acid hydrolysis 2 O 4 @ CN, the coordination unsaturated site center is constructed by means of acetate coordination, the dispersion degree of Co and Fe atoms is improved by CN loading, and meanwhile, a large number of coordination unsaturated active catalytic centers are introduced, so that the catalytic efficiency is improved.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. Based on CoFe 2 O 4 A preparation method of the @ CN AOP high-efficiency catalyst is characterized by comprising the following steps:
s1: mixing and stirring DMF and absolute ethyl alcohol to prepare a solvent A;
s2: dissolving iron acetate and cobalt acetate in the solvent A, and stirring until the iron acetate and the cobalt acetate are completely dissolved to prepare a solution B;
s3: dissolving 2-amino terephthalic acid in the solution B, and stirring until the 2-amino terephthalic acid is completely dissolved to obtain a solution C;
s4: carrying out hydrothermal reaction on the solution C, washing and drying to obtain a powder sample D;
s5: after vacuum drying, the powder sample D is calcined in an air atmosphere to obtain a powder based on CoFe 2 O 4 An AOP high efficiency catalyst of @ CN.
2. CoFe-based alloy according to claim 1 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst is characterized in that in S1, DMF and absolute ethyl alcohol are mixed according to the ratio of 4:1 to 1:4 by volume.
3. CoFe-based alloy according to claim 1 2 O 4 A preparation method of the @ CN AOP high-efficiency catalyst is characterized in that in S2, 0.6-2 mmol of ferric acetate and 0.3-1 mmol of cobalt acetate are dissolved in 20mL of solvent A and stirred until the ferric acetate and the cobalt acetate are completely dissolved to prepare solution B.
4. CoFe-based alloy according to claim 1 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst is characterized in that 0.9-3 mmol of 2-aminoterephthalic acid is dissolved in 20mL of solution B in S3, and the solution C is prepared after the 2-aminoterephthalic acid is completely dissolved by stirring.
5. CoFe-based alloy according to claim 1 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst is characterized in that in S4, the solution C is poured into a polytetrafluoroethylene lining, and is packaged by a stainless steel hot kettle for hydrothermal reaction, wherein the reaction temperature of the hydrothermal reaction is 150-180 ℃, and the reaction time is 18-24 h.
6. CoFe-based alloy according to claim 1 2 O 4 A method for preparing the @ CN AOP high-efficiency catalyst, which is characterized in that the catalyst is S4After the hydrothermal reaction is finished, washing the reaction product by using ethanol and deionized water, centrifuging the reaction product for 2 to 3 times respectively, and drying the reaction product to obtain a powder sample D.
7. CoFe-based alloy according to claim 1 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst is characterized in that in S5, a powder sample D is placed in a vacuum drying oven at a vacuum degree of 10 -3 Pa, 100-120 ℃, and drying for 8-12 h in vacuum.
8. CoFe-based alloy according to claim 1 2 O 4 The preparation method of the @ CN AOP high-efficiency catalyst is characterized in that the S5 is calcined in an air atmosphere, the calcination temperature is 400-700 ℃, and the calcination time is 2-3 h.
9. Based on CoFe 2 O 4 An AOP high-efficiency catalyst of @ CN, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868332A (en) * | 2017-02-20 | 2017-06-20 | 安徽农业大学 | A kind of methods and applications that transition metal alloy is prepared based on metal organogel |
| CN108325565A (en) * | 2018-02-01 | 2018-07-27 | 山西大学 | Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application |
| CN109585825A (en) * | 2018-11-28 | 2019-04-05 | 成都理工大学 | The Ni/NiFe of bimetallic MOF precursor synthesis2O4Lithium ion battery negative material and preparation method thereof |
| CN109621962A (en) * | 2018-12-06 | 2019-04-16 | 广东省石油与精细化工研究院 | A kind of regular morphology metal oxide catalyst and its preparation method and application for eliminating formaldehyde |
| CN110265667A (en) * | 2019-06-12 | 2019-09-20 | 青岛科技大学 | A kind of novel nano composite catalyst and preparation method thereof applied to hydrogen reduction |
| CN213771876U (en) * | 2020-08-31 | 2021-07-23 | 苏州纳创佳环保科技工程有限公司 | Preparation device of porous metal oxide/carbon composite material |
-
2022
- 2022-12-28 CN CN202211700666.9A patent/CN115845903A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868332A (en) * | 2017-02-20 | 2017-06-20 | 安徽农业大学 | A kind of methods and applications that transition metal alloy is prepared based on metal organogel |
| CN108325565A (en) * | 2018-02-01 | 2018-07-27 | 山西大学 | Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application |
| CN109585825A (en) * | 2018-11-28 | 2019-04-05 | 成都理工大学 | The Ni/NiFe of bimetallic MOF precursor synthesis2O4Lithium ion battery negative material and preparation method thereof |
| CN109621962A (en) * | 2018-12-06 | 2019-04-16 | 广东省石油与精细化工研究院 | A kind of regular morphology metal oxide catalyst and its preparation method and application for eliminating formaldehyde |
| CN110265667A (en) * | 2019-06-12 | 2019-09-20 | 青岛科技大学 | A kind of novel nano composite catalyst and preparation method thereof applied to hydrogen reduction |
| CN213771876U (en) * | 2020-08-31 | 2021-07-23 | 苏州纳创佳环保科技工程有限公司 | Preparation device of porous metal oxide/carbon composite material |
Non-Patent Citations (1)
| Title |
|---|
| 刘艳茹: ""MOFs衍生的CoFe2O4@掺N碳材料催化PMS去除诺氟沙星和磺胺甲恶唑"", 万方数据知识服务平台, pages 13 * |
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