CN115228487B - FeSe2Fenton-like catalyst @ C and preparation method and application thereof - Google Patents
FeSe2Fenton-like catalyst @ C and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000002872 contrast media Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002356 single layer Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 7
- 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 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 6
- YVPYQUNUQOZFHG-UHFFFAOYSA-N amidotrizoic acid Chemical group CC(=O)NC1=C(I)C(NC(C)=O)=C(I)C(C(O)=O)=C1I YVPYQUNUQOZFHG-UHFFFAOYSA-N 0.000 claims description 6
- 229960005223 diatrizoic acid Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 10
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- -1 transition metal selenide Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 239000013274 2D metal–organic framework Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
-
- 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
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- 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
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- 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
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- 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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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention discloses a FeSe 2 @C Fenton catalyst, a preparation method and application thereof, wherein FeSe 2 particles in the active center of the catalyst are uniformly dispersed in a porous carbon grid, and a nano cubic lattice formed by closely stacking porous carbon grids in a single layer form a two-dimensional superlattice structure; the preparation method comprises the following steps: mixing Fe 3O4 @C with selenium powder, and calcining at 350-380 ℃ in the atmosphere of mixed gas of H 2 and inert gas to carry out selenization to obtain FeSe 2 @C Fenton catalyst; the porous two-dimensional superlattice structure characteristic of the FeSe 2 @C Fenton-like catalyst is beneficial to reducing catalyst aggregation and mass transfer resistance, more active sites can be exposed, metal ion dissolution is reduced, and the catalytic efficiency is improved; the catalyst is used for degrading the iodized X-ray contrast agent, does not need the conditions of light addition, heating and the like, reduces the difficulty of practical application, and is beneficial to large-scale use.
Description
Technical Field
The invention relates to a catalyst, in particular to a FeSe 2 @C Fenton catalyst, and a preparation method and application thereof.
Background
The transition metal selenide is used as an emerging nano material, and has been widely applied to electrode materials such as energy conversion and energy storage due to the excellent physical and chemical properties. Particularly, feSe 2 has been paid attention to because of its excellent redox activity and durability, and polyvalent selenium ions have a strong electron donating ability, so that oxidation-reduction of adjacent metals can be promoted to some extent, thereby affecting the progress of the whole reaction. Previous studies have prepared nanoscale FeSe 2 and iron-based metal organic framework-derived FeSe 2 @C catalysts for use in the degradation of organic contaminants by activated persulfates. However, the material still has the problems of less active sites, larger mass transfer resistance, poor conductivity, lower specific surface area, fe 3+/Fe2+ circulation rate and the like caused by easy agglomeration of the catalyst, so that the catalytic degradation efficiency is still not ideal.
Disclosure of Invention
The invention aims to: the first aim of the invention is to provide a FeSe 2 @C Fenton catalyst which is not easy to agglomerate, has high surface area and high catalytic activity; a second object of the present invention is to provide a process for preparing the catalyst; a third object of the present invention is to provide the use of the catalyst for the degradation of iodinated X-ray contrast agents.
The technical scheme is as follows: the FeSe 2 @C Fenton-like catalyst disclosed by the invention has the advantages that active center FeSe 2 particles are uniformly dispersed in a porous carbon grid, and a two-dimensional superlattice structure is formed by closely stacking nano cubic lattices of a single layer of the porous carbon grid.
The preparation method of the FeSe 2 @C Fenton-like catalyst comprises the following steps: mixing Fe 3O4 @C with selenium powder, and calcining at 350-380 ℃ in the mixed gas atmosphere of H 2 and inert gas to carry out selenization to obtain the FeSe 2 @C Fenton catalyst.
The Fe 3O4 @C and the selenium powder are selenized in the calcining process to generate FeSe 2 @C; the addition of hydrogen in an inert atmosphere can further prevent oxidation of the metal surface.
Preferably, the mass ratio of the Fe 3O4 @C to the selenium powder is 1:2-5; the selenization degree of FeSe2@C is affected by different mass ratios, and the efficiency of degrading organic pollutants by iron-activated persulfate is affected by the anionic selenium of FeSe2@C with different selenization degrees.
Preferably, the calcination time is 7 to 8 hours.
Preferably, the calcination temperature rise rate is 4-7 ℃/min.
The preparation method of the Fe 3O4 @C comprises the following steps: (1) Ferric chloride hexahydrate is dissolved in water and then mixed with sodium oleate for aging; (2) Adding sodium sulfate, mixing, and calcining in an N 2 atmosphere to obtain Fe 3O4 @C; wherein the mass ratio of the ferric chloride hexahydrate to the sodium oleate to the sodium sulfate is 18:60-75:500-600.
Preferably, in the step (1), the aging temperature is 84-87 ℃ and the aging time is 2.5-4 hours. In the aging process, sodium oleate is dissolved and then reacts with ferric chloride hexahydrate to produce ferric oleate.
Preferably, in the step (2), the calcination temperature is 580-640 ℃ and the calcination time is 2.5-4 hours. The mixture of the iron oleate and the sodium sulfate is calcined at high temperature to generate Fe 3O4 @C.
The FeSe 2 @C Fenton-like catalyst is applied to degradation of iodized X-ray contrast agents.
The application method specifically comprises the following steps: uniformly dispersing the prepared catalyst in a diatrizoic acid solution, stirring in a dark place to ensure that the catalyst reaches adsorption-desorption equilibrium, and adding persulfate to initiate catalytic degradation reaction to degrade.
The mechanism of the invention is as follows: the invention adopts FeSe 2 with double active centers as Fenton-like catalyst, and the two-dimensional porous FeSe 2 @C nanocrystalline superlattice catalyst is obtained by uniformly limiting FeSe 2 particles in a porous carbon grid, and the porous two-dimensional superlattice structure characteristics not only help to reduce catalyst agglomeration and mass transfer resistance, but also can expose more active sites and reduce metal ion dissolution. In addition, the FeSe 2 @C Fenton-like catalyst with the optimal selenium content is finally determined by further controlling the selenium content in FeSe 2 @C.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The porous two-dimensional superlattice structure characteristic of the FeSe 2 @C Fenton-like catalyst is beneficial to reducing catalyst aggregation and mass transfer resistance, more active sites can be exposed, metal ion dissolution is reduced, electron transmission is fast, and catalytic efficiency is improved; (2) The preparation method is prepared by a calcination method, has the advantages of simple and easily obtained raw materials, low price, no pollution, environment friendliness, simple preparation process, mild preparation conditions and easy realization of large-scale production; (3) The catalyst is used for degrading the iodized X-ray contrast agent, does not need the conditions of light addition, heating and the like, reduces the difficulty of practical application, and is beneficial to large-scale use.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the catalysts prepared in examples 1 to 4 and comparative example 1;
FIG. 2 is a graph of the Raman spectra (RAMAN SPECTRA) of the catalysts prepared in examples 1-4;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the catalyst prepared in example 2;
FIG. 4 is a Transmission Electron Microscope (TEM) image of the catalyst prepared in example 2;
FIG. 5 is a high-power transmission electron micrograph (HRTEM) of the catalyst prepared in example 2;
FIG. 6 is an Atomic Force Microscope (AFM) image of the catalyst prepared in example 2;
FIG. 7 is a graph showing the effect of the persulfates activated to degrade diatrizoic acid in examples 1-4, comparative example 1 and FeSe 2;
fig. 8 is a graph showing the cycle stability test of the catalyst prepared in example 2.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
The preparation method of the FeSe 2 @C Fenton-like catalyst comprises the following steps of:
(1) Preparation of Fe 3O4 @ C
0.72G of ferric chloride hexahydrate is dissolved in 2ml of deionized water, then 2.44g of sodium oleate is fully mixed with the ferric chloride hexahydrate, the obtained mixture is aged for 3 hours at 85 ℃, then is uniformly mixed with 20g of sodium sulfate powder, then the mixture is calcined for 3 hours in an N 2 atmosphere at 600 ℃, after natural cooling, the mixture is washed for 3 times by the deionized water, and is dried for 6 hours at 100 ℃ to obtain Fe 3O4 @C.
(2) Preparation of FeSe 2 @ C
50Mg of Fe 3O4 @C and 100mg of selenium powder are weighed, uniformly mixed and placed in a quartz boat, the quartz boat is transferred into a tube furnace, and selenization is carried out for 7H at 350 ℃ under the atmosphere of H 2/Ar (5 vol% of H 2) at the heating rate of 4 ℃/min. And cooling the tubular furnace to room temperature to obtain the FeSe 2 @C Fenton catalyst.
Example 2
(1) Fe 3O4 @ C was prepared as in example 1.
(2) Preparation of FeSe 2 @ C
50Mg of Fe 3O4 @C and 150mg of selenium powder are weighed, uniformly mixed and placed in a quartz boat, the quartz boat is transferred into a tube furnace, and selenization is carried out for 8 hours at 360 ℃ under the atmosphere of H 2/Ar (5 vol% of H 2) at the heating rate of 5 ℃/min. And cooling the tubular furnace to room temperature to obtain the FeSe 2 @C Fenton catalyst.
Example 3
(1) Fe 3O4 @ C was prepared as in example 1.
(2) Preparation of FeSe 2 @ C
50MgFe 3O4 @C and 200mg selenium powder were weighed and mixed uniformly in a quartz boat, the quartz boat was transferred to a tube furnace, and selenization was performed at 370℃for 7.5 hours at a heating rate of 6℃per minute under an atmosphere of H 2/Ar (5 vol% H 2). And cooling the tubular furnace to room temperature to obtain the FeSe 2 @C Fenton catalyst.
Example 4
(1) Fe 3O4 @ C was prepared as in example 1.
(2) Preparation of FeSe 2 @ C
50Mg of Fe 3O4 @C and 250mg of selenium powder are weighed, uniformly mixed and placed in a quartz boat, the quartz boat is transferred into a tube furnace, and selenium is carried out for 7.8 hours at 380 ℃ under the heating heat rate of 7 ℃/min under the atmosphere of H 2/Ar(5vol％H2). And cooling the tubular furnace to room temperature to obtain the FeSe 2 @C Fenton catalyst.
Comparative example 1
The mass ratio of Fe 3O4 @C to selenium powder was changed to 1:1 on the basis of example 1, with the other conditions unchanged.
Characterization of Performance
X-ray diffraction (XRD) characterization was performed on the catalysts of different materials prepared in examples 1 to 4 and comparative example 1, and as shown in FIG. 1, characteristic peaks of FeSe 2 appear in XRD patterns of examples 1 to 4 and are consistent with the wustite standard card (JCPDS No. 74-0247); in the XRD pattern of comparative example 1, there are some impurity peaks in addition to the characteristic peaks of FeSe 2.
The catalysts prepared in examples 1-4 were subjected to raman spectroscopic characterization, as shown in fig. 2, at 218.1cm -1,282.3cm-1,592.2cm-1, corresponding to the characteristic peak of FeSe 2, further confirming the successful preparation of FeSe 2 in the catalysts of examples 1-4, and on the other hand, the presence of carbon material. The above results indicate that FeSe 2 @ C of examples 1-4 was successfully prepared.
The catalyst prepared in example 2 was characterized by using a field emission scanning electron microscope (FSEM) and a Transmission Electron Microscope (TEM), and the results are shown in fig. 3 to 4. It can be seen from fig. 3 that the prepared FeSe 2 @c consisted of a two-dimensional lamellar structure consisting of a single layer of closely packed nanocube lattice, which was rough in surface and rich in porous structure. The nano-squares on the FeSe 2 @C surface of FIG. 4 are ordered.
Characterization of the catalyst prepared in example 2 using a high-power transmission microscope shows that, as shown in fig. 5, the active center FeSe 2 particles are uniformly dispersed in the porous carbon grid, and because the FeSe 2 particles are confined in the carbon grid, agglomeration of FeSe 2 particles can be effectively prevented and metal ion dissolution can be reduced.
The catalyst prepared in example 2 was characterized by an atomic force microscope, and as shown in fig. 6, it can be seen that the FeSe 2 @ C nanocube superlattice is a two-dimensional layered nanosheet structure, and based on the height distribution, the total thickness is about 48.05nm, which further proves that the porous carbon network single-layer tightly packed nanocube lattice forms a two-dimensional superlattice structure.
Application of
The application of the catalyst FeSe 2 @C Fenton-like catalyst in degrading iodized X-ray contrast agent is particularly applied to degrading diatrizoic acid, and the application method comprises the following steps:
(1) Uniformly dispersing 10mg of catalyst in 50mL of diatrizing acid solution with the concentration of 20mg/L, and stirring for 20min in a dark place to establish adsorption-desorption balance;
(2) Adding 800 mu L of Peroxymonosulfate (PMS) into the system to initiate catalytic degradation reaction;
(3) Taking out 0.8mL of reaction solution at the time points of 1,3, 5, 7, 9, 15 and 20min respectively;
(4) The reaction solution was filtered through a 0.22 μm nylon filter membrane, quenched with 0.2mL of methanol, and terminated;
(5) Undegraded diatrizoic acid was detected by high performance liquid chromatography at λ=254 nm.
The degradation effects of the catalysts prepared in examples 1-4 and comparative example 1 and the degradation effects of FeSe 2 are shown in FIG. 7, the degradation rates of the catalyst to diatrizoic acid in 20min are 52.2%, 100.0%, 94.8%, 60.7%, 42.2% and 38.4%, respectively, and the catalytic effects of the FeSe 2 @C catalysts prepared in examples 1-4 are better than that of FeSe 2, because on one hand, the porous and two-dimensional layered structure of the FeSe 2 @C two-dimensional superlattice structure is beneficial to reducing catalyst agglomeration and mass transfer resistance and also exposes more active sites; selenium, on the other hand, not only activates persulfate-producing active species, but also provides electrons to promote the reduction of Fe 3+ to Fe 2+. Wherein, in the embodiment 2, the mass ratio of Fe 3O4 @C to selenium powder is optimal, the selenization degree of the prepared FeSe 2 @C catalyst is best, and the catalytic effect is optimal. Comparative example 1 the proportion of selenium was reduced on the basis of example 1 and the catalytic effect was reduced due to the low degree of selenization.
The catalyst prepared in example 2 was subjected to a cycle stability test, test method: in the cycle stability test, after each catalytic degradation experiment was completed, the catalyst was collected, washed with ethanol and water sufficiently and dried, and then the next catalytic degradation experiment was performed, and the results are shown in fig. 8. It can be seen from fig. 8 that after four consecutive runs of the catalyst, the removal rate decreased slightly from 100.0% to 84.1%, mainly due to the surface of the FeSe 2 @ C nanocube superlattice covered by the degradation intermediate of DIA. Overall, the catalyst still shows greater stability and good recyclability.
Claims (6)
1. The application of a FeSe 2 @C Fenton catalyst in degrading an iodinated X-ray contrast agent is characterized in that the contrast agent is diatrizoic acid; the FeSe 2 particles in the active center of the catalyst are uniformly dispersed in a porous carbon grid, and the nano cubic lattice formed by closely stacking the porous carbon grid single layers forms a two-dimensional superlattice structure;
The preparation method of the catalyst comprises the following steps: mixing Fe 3O4 @C with selenium powder, and calcining at 350-380 ℃ in the atmosphere of mixed gas of H 2 and inert gas to carry out selenization to obtain FeSe 2 @C Fenton catalyst; wherein the mass ratio of Fe 3O4 @C to selenium powder is 1:2-5;
The preparation method of the Fe 3O4 @C comprises the following steps: (1) Ferric chloride hexahydrate is dissolved in water and then mixed with sodium oleate for aging; (2) Adding sodium sulfate, mixing, and calcining in an N 2 atmosphere to obtain Fe 3O4 @C; wherein the mass ratio of the ferric chloride hexahydrate to the sodium oleate to the sodium sulfate is 18:60-75:500-600.
2. The use according to claim 1, wherein in the preparation of the catalyst, the calcination time is 7-8 hours.
3. The use according to claim 1, wherein in the preparation method of the catalyst, the calcination heating rate is 4-7 ℃/min.
4. The use according to claim 1, wherein in step (1) of the preparation method of Fe 3O4 @ C, the aging temperature is 84-87 ℃ and the aging time is 2.5-4 hours.
5. The method according to claim 1, wherein in the step (2) of the preparation method of Fe 3O4 @C, the calcination temperature is 580-640 ℃ and the calcination time is 2.5-4 hours.
6. The use according to claim 1, characterized in that the application method is: uniformly dispersing the prepared catalyst in an iodized X-ray contrast agent solution, stirring in a dark place to ensure that the catalyst reaches adsorption-desorption equilibrium, and adding persulfate to initiate catalytic degradation reaction to degrade.
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| CN104993126A (en) * | 2015-07-28 | 2015-10-21 | 河北工业大学 | Preparation method and application of carbon-coated Fe3O4 nanoparticle lithium ion battery negative electrode material |
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
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| CN104993126A (en) * | 2015-07-28 | 2015-10-21 | 河北工业大学 | Preparation method and application of carbon-coated Fe3O4 nanoparticle lithium ion battery negative electrode material |
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
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