CN117380222A - Fe (Fe) 3 S 4 Preparation method and application of derivative catalyst - Google Patents
Fe (Fe) 3 S 4 Preparation method and application of derivative catalyst Download PDFInfo
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- CN117380222A CN117380222A CN202311361955.5A CN202311361955A CN117380222A CN 117380222 A CN117380222 A CN 117380222A CN 202311361955 A CN202311361955 A CN 202311361955A CN 117380222 A CN117380222 A CN 117380222A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 39
- 230000015556 catabolic process Effects 0.000 claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013216 MIL-68 Substances 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 27
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 4
- 238000001212 derivatisation Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 75
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 239000004021 humic acid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004753 textile Substances 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
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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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- 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
-
- 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
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses Fe 3 S 4 A process for preparing derivative catalyst by adding ferric chloride hexahydrate and 1, 4-terephthalic acid to N, N-dimethylformamide, reacting at 97-102 deg.C for 118-120 hr,solid-liquid separation, washing the solid by N, N-dimethylformamide and acetone in sequence, and vacuum drying to obtain the MIL68- (Fe) catalyst; placing MIL-68 (Fe) catalyst and thioacetamide in absolute ethanol, performing ultrasonic treatment at 25-40deg.C for 25-35min, placing at 110-150deg.C for reaction for 14-18 hr, cooling to room temperature, centrifuging, washing the solid with absolute ethanol and deionized water sequentially, and vacuum drying to obtain Fe 3 S 4 The derivative catalyst has excellent degradation effect in the degradation of dye rhodamine B by the activated oxidant, the degradation efficiency can reach 100 percent, the catalyst has certain magnetism, and the catalyst can be separated by an external magnet in a water body solution, so that the problem of difficult recovery can be solved.
Description
Technical Field
The invention relates to Fe 3 S 4 A preparation method and application of a derivative catalyst, belonging to the technical field of water purification materials.
Background
Water pollution by organic pollutants has been a serious problem in the industrial fields of paint, textile, leather, paper, cosmetics, chemical processing and the like. These organic contaminants are highly toxic and chromatic and pose a significant threat to the water ecosystem and human health. Thus, there is a great need for an efficient, rapid, and safe method for removing organic dye contaminants from wastewater.
Previous studies have shown that traditional water treatment methods, such as adsorption, biological treatment, and membrane filtration, can effectively remove dye contaminants from wastewater. However, these techniques are often inefficient and prone to secondary contamination. The traditional advanced oxidation treatment technology mainly depends on homogeneous activation of light energy, heat energy or transition metal, and the like, usually requires additional energy input, and some transition metal centers have certain toxicity, so that the metal ion leaching problem is easily caused in the activation process, and secondary pollution is caused to the environment. Advanced oxidation technologies (AOPs), which are activated by catalysts to produce substances with strong oxidation activity, are receiving great attention to mineralize organic pollutants into low-toxicity harmless small molecules, carbon dioxide and water, and are considered as a technology for degrading organic pollutants in water environment particularly efficiently. Therefore, the development of a catalyst that is environmentally friendly and has high efficiency is one of the current research hotspots.
Metal-organic frameworks (MOFs) have become a promising catalyst because of their large surface area and abundant active sites and tunable structures, and can be used as precursors to prepare different catalyst materials, and transition metal centers in MOFs can be used as reactive sites; preparation of Fe by MIL-68 (Fe) at present 3 S 4 Research or patents for degrading organic pollutants in wastewater by using advanced oxidation technology to generate free radicals have not been reported yet.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides Fe 3 S 4 The preparation method of the derivative catalyst aims at solving the problems that the active sites of some heterogeneous catalysts are insufficient, extra energy input is needed in the actual catalytic process, the rhodamine B dye degradation efficiency in wastewater is low, the catalyst is difficult to recover, the price is high, secondary pollution is easy to cause, the consumption of an oxidant is high and the like; fe prepared by the invention 3 S 4 The derived catalyst has extremely high RhB degradation efficiency, simple catalyst recovery, no need of extra energy consumption and no secondary pollution.
Fe of the present invention 3 S 4 The preparation method of the derivative catalyst comprises the following steps:
(1) Adding ferric chloride hexahydrate and 1, 4-terephthalic acid into N, N-dimethylformamide, reacting for 118-120h at 97-102 ℃, carrying out solid-liquid separation, washing the solid by the N, N-dimethylformamide and acetone in sequence, and carrying out vacuum drying to obtain an MIL-68 (Fe) catalyst;
the mass ratio of the ferric chloride hexahydrate to the 1, 4-terephthalic acid is 1:1-3;
(2) Placing MIL-68 (Fe) catalyst and thioacetamide in absolute ethanol, performing ultrasonic treatment at 25-40deg.C for 25-35min, placing at 108-113 deg.C for reaction for 14-18 hr, cooling to room temperature, centrifuging, washing the solid with absolute ethanol and deionized water sequentially, and vacuum drying to obtain Fe 3 S 4 A derivatizing catalyst;
the mass ratio of the MIL-68 (Fe) catalyst to the thioacetamide is 1:3-5.
The ultrasonic power is 50-150W.
Another object of the present invention is Fe obtained by the above method 3 S 4 The derivative catalyst is applied to degradation of dye rhodamine B in water, wherein Peroxymonosulfate (PMS), peroxydisulfate (PDS), hydrogen peroxide or peracetic acid (PAA) are added in degradation.
The beneficial effects of the invention are as follows:
(1) The invention takes a nontoxic iron-based metal organic framework (MIL-68 (Fe)) as a template, and prepares the derivative Fe through ligand exchange with thioacetamide 3 S 4 The catalyst is layered, has larger specific surface area, larger specific surface area and layered structure, can obviously shorten the distance of free radical diffusion, provides more active sites for the conversion of organic pollutants, and greatly improves the interaction between the organic pollutants and the catalyst;
(2) Accelerating the conversion of Fe (III) and Fe (II) and increasing the number of persistent unsaturated Fe sites is a key to improving the performance of Fe-MOFs, and the invention takes thioacetamide as an S source, and introduces unsaturated S atoms as electron donors to facilitate Fe 3+ /Fe 2+ Cycling;
(3) The catalyst derived from MIL-68 (Fe) serving as a precursor has super-strong magnetism, and can be recovered in water through an external magnet, so that the problem of difficult catalyst recovery is solved;
(4) The preparation method of the invention is simple, easy to operate and the catalyst is environment-friendly. The catalyst has extremely high activation effect on different oxidants such as peroxymonosulfate, peroxydisulfate, hydrogen peroxide and the like in the advanced oxidation technology; namely, has excellent degradation performance on rhodamine B, and is characterized by Fe 3 S 4 The degradation efficiency of the PDS system can reach 100% in 5 min; at Fe 3 S 4 The degradation efficiency of the PMS system in 5min can reach 94%; at Fe 3 S 4 /H 2 O 2 The degradation efficiency of the system can reach 88% after 5 min. Has high application potential in the aspect of dye wastewater remediation.
Drawings
FIG. 1 is Fe 3 S 4 Hysteresis loop (VSM) diagram of the derivative catalyst;
FIG. 2 is Fe 3 S 4 Scanning Electron Microscope (SEM) images of the derived catalysts;
FIG. 3 is a template-free Fe 3 S 4 Scanning Electron Microscope (SEM) images of the catalyst;
FIG. 4 is Fe 3 S 4 An X-ray diffraction (XRD) pattern of the derivative catalyst;
FIG. 5 is Fe 3 S 4 N of the derived catalyst 2 Adsorption-desorption isotherm plot;
FIG. 6 is Fe 3 S 4 Thermogravimetric (TGA) profile of the derivative catalyst;
FIG. 7 is a diagram of Fe in a body of water 3 S 4 The activation effect of the derivative catalyst on different oxidants;
FIG. 8 shows the Fe content in water 3 S 4 The degradation result of rhodamine B by the derivative catalyst;
FIG. 9 shows the degradation effect of PDS on rhodamine B in water at different dosages;
FIG. 10 is a graph showing the degradation results of rhodamine B by different catalysts, wherein Fe is shown in the graph 3 S 4 Is Fe 3 S 4 Derivatizing catalyst
FIG. 11 shows Fe at different pH values in a water body 3 S 4 The effect of the derivative catalyst on rhodamine B degradation;
FIG. 12 shows Fe at different humic acid concentrations in water 3 S 4 Graph of the effect of the derived catalyst on rhodamine B degradation.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1
1. The Fe is 3 S 4 The preparation method of the derivative catalyst comprises the following steps:
(1) 1.351g of ferric chloride hexahydrate and 1.66g of 1, 4-terephthalic acid are added into 60mL of N, N-dimethylformamide, the mixture is reacted for 120h at 100 ℃, solid-liquid separation is carried out, the solid is washed by N, N-dimethylformamide and acetone in sequence, and vacuum drying is carried out at 100 ℃ to prepare an MIL-68 (Fe) catalyst;
(2) Placing 0.5g MIL-68 (Fe) and 2g thioacetamide into 80mL of absolute ethanol, performing ultrasonic treatment at 30deg.C and 50W for 30min, reacting at 110deg.C for 16h, cooling to room temperature, centrifuging, washing the solid with absolute ethanol and deionized water sequentially, and vacuum drying at 60deg.C to obtain Fe 3 S 4 A derivatizing catalyst;
detection of Fe prepared in this example by hysteresis loop test 3 S 4 The saturation magnetization value of the derivative catalyst is 28.9emu/g, the derivative catalyst has stronger magnetism, and can be recovered through an external magnet in a water body, so that the problem of difficult catalyst recovery is solved, and the hysteresis loop diagram is shown in figure 1.
Reference is made simultaneously to "Zhang, j et al Humic acid promoted activation of peroxymonosulfate by Fe (3) S (4) for degradation of 2,4,6-trichlorophenol: An experimental and theoretical study.Template-free Fe prepared by J Hazard Mater 2022.434:p. 128913 middle method 3 S 4 The catalyst served as a control;
fe prepared in this example 3 S 4 Derived catalyst, template-free Fe 3 S 4 The scanning electron microscope of the catalyst is shown in fig. 2 and 3, and Fe is shown in fig. 2 3 S 4 The morphology is lamellar, consists of nano-sheets and has no template Fe 3 S 4 The surface of the catalyst is smooth; the layered structure is favorable for shortening the ion diffusion distance and providing more active sites for the conversion of the oxidant, thereby obviously improving Fe 3 S 4 The interaction between the derivative catalyst and the oxidant improves the degradation efficiency of the RhB.
Fe prepared in this example 3 S 4 XRD patterns of the derived catalyst are shown in FIG. 4, and it can be seen from FIG. 4 that the precursor MIL-68 (Fe) and the derived Fe 3 S 4 The crystallinity of the catalyst is better, and the prepared Fe 3 S 4 The main peak position of the catalyst was consistent with standard card No. 16-173, indicating successful preparation of the derivative material.
Example Fe 3 S 4 N of the derived catalyst 2 The adsorption-desorption isotherm diagram is shown in figure 5, and MIL-68 (Fe) ratio tableArea is about 301m 2 G, similar to literature reports; fe (Fe) 3 S 4 The derivative catalyst has larger specific surface area and larger average pore diameter, and is beneficial to the exposure of active sites.
Example Fe 3 S 4 The thermogravimetric diagram of the derived catalyst is shown in FIG. 6, and it can be seen from FIG. 6 that the thermal stability of MIL-68 (Fe) can reach 384 ℃, and the derived Fe 3 S 4 The thermal stability is greatly improved and can reach 527 ℃, which shows that the thermal stability of the derivative material is higher than that of the precursor MOFs material.
2. Fe prepared in this example 3 S 4 The derivative catalyst is used for activating performance test of rhodamine B in persulfate degradation water body: fe is added according to the adding proportion of 0.15g/L 3 S 4 The derivative catalyst is put into 50mL rhodamine B solution with the concentration of 15mg/L, and is rapidly stirred for 30min at 600rpm to reach adsorption-desorption equilibrium, and PDS and PMS are respectively put into the catalyst according to the proportion of 0.4mmol/L、H 2 O 2 Taking the reaction solution, filtering with a 0.22 mu m filter head to obtain clear liquid at intervals in the reaction, and testing the residual rhodamine B amount in the clear liquid by an ultraviolet spectrophotometer;
as shown in FIG. 7, the results of FIG. 7 show that the degradation efficiency of the rhodamine B by the three oxidation systems within 5min can reach more than 88%, which proves that the catalyst has better activation effect on different oxidants, and the Fe of the embodiment exists in the presence of Peroxodisulfate (PDS) 3 S 4 The derivative catalyst has excellent degradation effect (5 min, 100%) on rhodamine B, and Fe in water 3 S 4 The derivative catalyst has good activating effect on different oxidants.
3. Adding Fe at a ratio of 0.05g/L, 0.1g/L, 0.15g/L, 0.2g/L, 0.25g/L to 15mg/L rhodamine B solution 3 S 4 Deriving the catalyst, adding PDS, and the rest conditions are the same as those in the step 2, and the result is shown in figure 8, wherein when the catalyst dosage is 0.15g/L, the degradation rate of rhodamine B in 5min is 100% as shown in figure 8;
4. adding Fe into 15mg/L rhodamine B solution according to the proportion of 0.15g/L 3 S 4 The derived catalyst is used for detecting the degradation effect of PDS on rhodamine B with different dosages, the result is shown in figure 9, and the result is shown in figure 9When the PDS addition amount is 0.2mmol/L, the degradation rate of rhodamine B in 5min is 98.1 percent; when the PDS addition amount is 0.4mmol/L, the degradation rate of rhodamine B in 5min is 100%; when the PDS addition amount is 0.6mmol/L, the degradation rate of rhodamine B in 5min is 98.6%; when the PDS addition amount is 0.8mmol/L, the degradation rate of rhodamine B in 5min is 98.9%; when the PDS addition amount is 1mmol/L, the degradation rate of rhodamine B in 5min is 98.9%;
5. PDS and Fe are respectively added into 15mg/L rhodamine B solution 3 S 4 Derivatization catalyst, fe 3 S 4 Derived catalyst+PDS, MIL-68 (Fe) catalyst+PDS, template-free Fe 3 S 4 catalyst+PDS, setting blank control without catalyst, wherein the adding amount of PDS is 0.4mmol/L, and other catalysts are added according to the proportion of 0.15 g/L;
the results of rhodamine B degradation are shown in FIG. 10, and the Fe prepared in the embodiment can be seen from the graph 3 S 4 The effect of the derivative catalyst in catalyzing and degrading rhodamine B is obviously higher than that of other reagents.
6、Fe 3 S 4 According to the degradation experiment of the derivative catalyst (0.15 g/L) on rhodamine B solution with 15mg/L and different pH values (2-10), the PDS addition amount is 0.4mmol/L, the rest conditions are the same as those in step 2, the result is shown in figure 11, and as can be seen from figure 11, the derivative catalyst still has good degradation effect on rhodamine B within the pH value of 2-10, so that the application range of the pH value of the derivative catalyst is wider.
7. Humic acid is widely used as natural organic substances in the natural world, has a non-negligible effect on degradation, and is Fe 3 S 4 The derived catalyst degrades rhodamine B solution containing humic acid (0-40 mg/L) with 15mg/L, the PDS addition amount is 0.4mmol/L, and the result is shown in figure 12, and the figure 12 shows that in the rhodamine B solution containing humic acid with different concentrations, the humic acid has little influence on the degradation of rhodamine B by the catalyst activated peroxodisulfate.
Example 2
(1) Adding 1g of ferric chloride hexahydrate and 2g of 1, 4-terephthalic acid into 60mL of N, N-dimethylformamide, reacting at 97 ℃ for 120h, carrying out solid-liquid separation, washing the solid by the N, N-dimethylformamide and acetone in sequence, and carrying out vacuum drying at 100 ℃ to obtain an MIL-68 (Fe) catalyst;
(2) Placing 0.6g of MIL-68 (Fe) and 2g of thioacetamide into 80mL of absolute ethyl alcohol, performing ultrasonic treatment at 25 ℃ and 70W for 30min, performing reaction at 130 ℃ for 16h, cooling to room temperature, centrifuging, washing the solid sequentially by absolute ethyl alcohol and deionized water, and performing vacuum drying at 60 ℃ to obtain Fe 3 S 4 A derivatizing catalyst;
(3) Fe prepared in this example 3 S 4 Performance test of derivative catalyst for activating rhodamine B in PDS degradation water body
Fe is added according to the adding proportion of 0.15g/L 3 S 4 Putting the derivative catalyst into 50mL rhodamine B solution with the concentration of 15mg/L, rapidly stirring at 600rpm for 30min to reach adsorption-desorption balance, adding PDS (0.4 mM), taking the reaction solution, filtering with a 0.22 mu m filter head to obtain clear liquid, and testing the residual rhodamine B amount in the clear liquid by an ultraviolet spectrophotometer; the degradation efficiency of RhB is 97.3% at 5 min.
Example 3
(1) Adding 1g of ferric chloride hexahydrate and 3g of 1, 4-terephthalic acid into 60mL of N, N-dimethylformamide, reacting at 97 ℃ for 120h, carrying out solid-liquid separation, washing the solid by the N, N-dimethylformamide and acetone in sequence, and carrying out vacuum drying at 100 ℃ to obtain an MIL-68 (Fe) catalyst;
(2) Placing 0.4g of MIL-68 (Fe) and 2g of thioacetamide into 80mL of absolute ethyl alcohol, performing ultrasonic treatment at 35 ℃ and 70W for 30min, performing reaction at 150 ℃ for 16h, cooling to room temperature, centrifuging, washing the solid sequentially by absolute ethyl alcohol and deionized water, and performing vacuum drying at 60 ℃ to obtain Fe 3 S 4 A derivatizing catalyst;
(3) Fe prepared in this example 3 S 4 Performance test of derivative catalyst for activating rhodamine B in persulfate degradation water body
Fe is added according to the adding proportion of 0.15g/L 3 S 4 Putting the derivative catalyst into 50mL rhodamine B solution with the concentration of 15mg/L, rapidly stirring at 600rpm for 30min to reach adsorption-desorption balance, adding PDS (0.4 mM), taking the reaction solution, filtering with a 0.22 mu m filter head to obtain clear liquid, and testing the residual rhodamine B amount in the clear liquid by an ultraviolet spectrophotometer; the RhB degradation efficiency at 5min is91.5%。
Claims (6)
1. Fe (Fe) 3 S 4 The preparation method of the derivative catalyst is characterized by comprising the following specific steps:
(1) Adding ferric chloride hexahydrate and 1, 4-terephthalic acid into N, N-dimethylformamide, reacting for 118-120h at 97-102 ℃, carrying out solid-liquid separation, washing the solid by the N, N-dimethylformamide and acetone in sequence, and carrying out vacuum drying to obtain an MIL-68 (Fe) catalyst;
(2) Placing MIL-68 (Fe) catalyst and thioacetamide in absolute ethanol, performing ultrasonic treatment at 25-40deg.C for 25-35min, placing at 110-150deg.C for reaction for 14-18 hr, cooling to room temperature, centrifuging, washing the solid with absolute ethanol and deionized water sequentially, and vacuum drying to obtain Fe 3 S 4 And (3) deriving the catalyst.
2. Fe according to claim 1 3 S 4 A process for preparing a derivatisation catalyst, characterized in that: the mass ratio of the ferric chloride hexahydrate to the 1, 4-terephthalic acid is 1:1-3.
3. Fe according to claim 1 3 S 4 A process for preparing a derivatisation catalyst, characterized in that: the mass ratio of MIL-68 (Fe) catalyst to thioacetamide is 1:3-5.
4. Fe according to claim 1 3 S 4 A process for preparing a derivatisation catalyst, characterized in that: and (3) the ultrasonic power in the step (2) is 50-150W.
5. The Fe of any one of claims 1 to 4 3 S 4 Preparation method of derivative catalyst prepared Fe 3 S 4 The application of the derivative catalyst in degrading dye rhodamine B.
6. The use according to claim 5, characterized in that: the degradation dye rhodamine B is added with peroxymonosulfate, peroxydisulfate, hydrogen peroxide or peroxyacetic acid.
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