CN113559883A - Preparation method of modified iron sulfide Fenton catalyst - Google Patents
Preparation method of modified iron sulfide Fenton catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 102
- 229910052960 marcasite Inorganic materials 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002715 modification method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- 238000006731 degradation reaction Methods 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 20
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000011028 pyrite Substances 0.000 description 6
- 239000012028 Fenton's reagent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000005580 Metazachlor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- STEPQTYSZVCJPV-UHFFFAOYSA-N metazachlor Chemical compound CC1=CC=CC(C)=C1N(C(=O)CCl)CN1N=CC=C1 STEPQTYSZVCJPV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
-
- 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
- C02F2305/026—Fenton's reagent
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
The invention discloses a preparation method of a modified iron sulfide Fenton catalyst, which comprises the following steps: weighing ferric salt and a sulfur source, placing the ferric salt and the sulfur source in a polytetrafluoroethylene tank, adding water, stirring, dissolving and uniformly mixing; heating to react, naturally cooling, washing and drying to obtain Fresh-FeS2(ii) a In the water vapor atmosphere, the obtained Fresh-FeS2Spread and dispersed on the heating part of the watch glassThen Heat-FeS is obtained2. FeS obtained by the invention2The Fenton-like catalyst has the advantages that the effect of catalyzing and degrading alachlor is obviously improved, the modification method is simple, convenient and quick, and environment-friendly, and the Fenton-like catalyst has good industrial application prospect in the aspect of removing alachlor organic pollutants in an environmental water sample.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a modified iron sulfide Fenton catalyst.
Background
The heterogeneous Fenton (Fenton) technology mainly means that a solid-phase iron-containing material is used as a Fenton reagent to degrade organic pollutants, and the catalytic process mainly occurs at a solid-liquid two-phase interface, so that Fe in a system is subjected to catalytic reaction2+The concentration requirement is low, thereby avoiding the generation of iron mud and H2O2The utilization rate is much higher than that of a homogeneous Fenton system. In addition, the heterogeneous Fenton reagent can degrade organic pollutants under the condition of being close to neutrality, meanwhile, the solid catalyst is easy to recover, the requirements on equipment, sites and subsequent maintenance in the treatment process are not high, and the cost benefit is high. Therefore, the heterogeneous Fenton technology is considered to be an organic pollutant removal method with great application prospect. Among various heterogeneous Fenton catalysts, iron-based materials have become one of the popular research objects in the field of organic pollutant degradation in recent years due to abundant raw material reserves and simple synthesis process.
Accordingly, researchers have performed a great deal of work, for example, iron-based heterogeneous Fenton catalytic materials such as iron ion supported materials, iron oxyhydroxide, iron oxides, etc. have been reported in turn to be used for efficient degradation of organic pollutants. Alachlor, a preemergence herbicide widely used in the world, is a ubiquitous dangerous and difficult-to-mineralize organic pollutant and is classified as a B2 carcinogen by the U.S. environmental protection agency. Pyrite type iron sulfide (FeS)2) The base Fenton reagent has catalytic degradation activity on degradation of organic pollutants, and is widely applied to the field of Fenton-like catalytic degradation. However, the existing synthesis of FeS2Although the synthetic process of the base Fenton reagent is simple and convenient, the environmental protection property and the catalytic activity of the base Fenton reagent can not meet the requirements of practical application, and the pyrite type FeS2The modification method of the Fenton-like catalyst has the defects of high energy consumption, complex process, addition of chemical reagents, high price and the like, so that the modified FeS with the industrial application prospect is developed2Fe-likeThe green and environment-friendly preparation method of the nton catalyst has great practical significance for removing organic pollutants such as alachlor and the like in an environmental water sample.
Disclosure of Invention
The invention aims to provide a green and environment-friendly preparation method of a modified iron sulfide Fenton catalyst, and the modified FeS2The Fenton-like catalyst has obviously improved metazachlor catalytic degradation effect, and has good industrial application prospect in the aspect of removing metazachlor organic pollutants in an environmental water sample.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a modified iron sulfide Fenton catalyst comprises the following steps:
(1) weighing ferric salt and a sulfur source, placing the ferric salt and the sulfur source in a polytetrafluoroethylene tank, adding water, stirring, dissolving and uniformly mixing;
(2) heating to react, naturally cooling, washing and drying to obtain Fresh-FeS2；
(3) In the water vapor atmosphere, the obtained Fresh-FeS2Spreading and dispersing on a watch glass, and heating to obtain Heat-FeS2。
According to the scheme, the sulfur source in the step (1) is sodium sulfite, sodium sulfide, thiourea or ammonium sulfide.
According to the scheme, the ferric salt in the step (1) is FeSO4.7H2O; the molar ratio of the ferric salt to the sulfur source is 1 (1-4).
According to the scheme, sulfur powder is added in the step (1), wherein the molar ratio of the ferric salt to the sulfur source to the sulfur powder is 1:1 (1-3).
According to the scheme, in the step (2), the temperature is increased to 140-200 ℃ for reaction for 24 hours.
According to the scheme, in the step (3), the mixture is heated to 80-95 ℃ and treated for 4-6 h.
Compared with the prior art, the invention has the following beneficial effects:
currently pyrite type FeS2The modification method of the Fenton-like catalyst has the defects of high energy consumption, complex flow, addition of other chemical reagents, high price and the like. The invention adopts a green, environment-friendly, simple and low-cost hydrothermal modification methodThe method prepares the pyrite type FeS with high catalytic activity2Fenton-like catalysts.
Experiments show that the degradation rate of alachlor degraded in a heterogeneous Fenton system is increased from less than 30 percent before modification to nearly 100 percent within 60min, and the degradation rate constant is (0.478 min)-1) Is unmodified Freeh-FeS2(0.021min-1) 23 times of the sample. Importantly, the modified FeS2The degradation rate constant of the Fenton-like catalyst is commercial pyrite (com-FeS)2) Degradation rate constant (0.0014 min)-1) 341 times higher.
FeS obtained by the invention2The Fenton-like catalyst has the advantages that the effect of catalyzing and degrading alachlor is obviously improved, the modification method is simple, convenient and quick, and environment-friendly, and the Fenton-like catalyst has good industrial application prospect in the aspect of removing alachlor organic pollutants in an environmental water sample.
Drawings
FIG. 1: Heat-FeS obtained in example 12With Fresh-FeS2The XRD pattern of (a); (b) SEM picture; (c) TEM and HRTEM images;
FIG. 2: Heat-FeS obtained in example 12With Fresh-FeS2EDS spectrum of (a); (b) XPS plots;
FIG. 3: Freeh-FeS obtained in example 12And Heat-FeS2(ii) an infrared spectrum;
FIG. 4: (a) a comparison graph of the degradation rates of alachlor in different systems; (b) a histogram of degradation rate constants;
FIG. 5: and (3) carrying out an Fe (II)/Fe (III) circulation mechanical drawing in the aerobic degradation process of the alachlor.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The invention provides a preparation method of a modified iron sulfide Fenton catalyst, which comprises the following specific steps:
(1) weighing ferric salt and a sulfur source, placing the ferric salt and the sulfur source in a polytetrafluoroethylene tank, adding water, stirring, dissolving and uniformly mixing; the sulfur source is sodium sulfite, sodium sulfide, thiourea or ammonium sulfide; the iron salt is FeSO4.7H2O; the molar ratio of the ferric salt to the sulfur source is 1 (1-4); or additionally adding sulfur powder, wherein the molar ratio of the ferric salt to the sulfur source to the sulfur powder is 1:1 (1-3);
(2) heating to 140-200 ℃ for reaction for 24h, naturally cooling, washing and drying to obtain Fresh-FeS2；
(3) In the water vapor atmosphere, the obtained Fresh-FeS2Spreading and dispersing on a watch glass, heating to 80-95 ℃ and treating for 4-6 h to obtain Heat-FeS2。
Example 1
FeSO (ferric oxide) is added4.7H2O, sodium thiosulfate and sulfur powder are mixed and dissolved in 60mL of purified water in a molar ratio of 1:1: 1. The mixture was stirred at room temperature for 0.5h, then heated at 200 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, washing and drying to obtain a sample of Fresh-FeS2. Then Fresh-FeS is added2Placing the sample in a glass vessel, placing in a constant temperature water bath at 85 deg.C, and heating in water vapor atmosphere for 6 hr to obtain Heat-FeS sample2。
FIG. 1 shows Freeh-FeS2And Heat-FeS2XRD, SEM, TEM and HRTEM images of (a). The Heat-FeS can be known by analyzing the XRD pattern2And Fresh-FeS2Diffraction peak signals are sharp, which shows that modified FeS and unmodified FeS can be obtained in crystal forms2However, Heat-FeS2The crystallinity is obviously better than that of Fresh-FeS2Shows that the modification by heat treatment is beneficial to improving FeS2The crystallinity of (2). Compared with the standard card, the Heat-FeS can be known2And Fresh-FeS2Are all face centered cubic structures. From the SEM picture, the prepared Fresh-FeS can be seen2Microspheres consisting essentially of smooth blocks with irregular surface sizes and a diameter of about 7 μm. While Heat-FeS2After heat treatment, the spherical structure is obviously sunken, and floccules appear on the surface. Heat-FeS can be seen in the TEM image2Is irregular in shape, and Fresh-FeS2Is in a micro-spherical shape. The results of HRTEM image of FIG. 1(c) in which the lattice spacing of 0.271nm is the pyrite (200) lattice plane demonstrate that pyrite-type FeS can be successfully synthesized by the preparation method of the present invention2。
From FIG. 2(a) EDS andas shown in Table 1, the results show that FeS2Consists of two elements, Fe and S, wherein the obvious O signal can be attributed to the oxidation of the surface of the material. As can be seen from Table 1, the thermally modified Heat-FeS2The content of oxygen element is obviously higher than that of Fresh-FeS2Higher, and lower S to Fe molar ratio from 1.68 to 1.27, the lower S/Fe ratio indicating a higher Fe content in the catalyst, which will favor the Fenton reaction for hydroxyl radical generation. As can be seen in FIG. 2(b) the high resolution spectrum of Fe 2p, Heat-FeS2The peak binding energy of Fe (II) -S on the phase surface is 710.1eV, which is obviously higher than that of Fresh-FeS2Fe (II) -S Peak binding energy (708.4eV) in the sample, indicating FeS after thermal modification2More Fe was exposed on the surface2+. In addition, two peaks at binding energies of 711.3eV and 713.4eV in the figure represent Fe, respectively3+And the presence of ferric sulfate, indicating FeS2An oxide layer is formed on the surface at the same time. In addition, the ratio of lattice ferrous iron to lattice ferric iron (Fe) can be obtained from the peak area of the 2p spectrum of Fe2+ lattice/Fetotal) And the ratio of surface ferrous iron to total iron (Fe)2+ surf/Fetotal) And the ratio of surface ferric iron to total iron (Fe)3+ surf/Fetotal). Heat-FeS can be known by fitting2Middle Fe2+ lattice/FetotalThe ratio is 0.470, which is obviously lower than Fresh-FeS20.755 of (1), in contrast, Heat-FeS2Fe (b) of2+ surf/FetotalThe ratio (0.292) is significantly higher than that of Fresh-FeS20.133 of (2), indicating Heat-FeS2The surface layer of the catalyst has more Fe2+This will help to promote the generation of hydroxyl radicals and the rapid degradation of alachlor. S2pShould correspond to S in the high-resolution spectra of (1), the peaks at 162.7eV, 163.8eV, and 164.4eV should correspond to S, respectively2 2-，Sn 2-(n>2) And S0Species of the species. Some weak peaks around 166.0eV belong to SO3 2-The binding energies 168.8eV and 170.0eV are determined as SO4 2-。Heat-FeS2Compare Fresh-FeS2The peak intensities at 168.8 and 170.0eV are significantly increased due to the hot steam modified post-FeS2The surface of the sample has onePartially oxidized to sulfate.
TABLE 1
From FIG. 3, Fresh-FeS2And Heat-FeS2Has substantially the same absorption peak at 601cm-1、670cm-1And 798cm-1The absorption peak is the expansion vibration peak of Fe-S. 1086cm-1And 1147cm-1The peak is the asymmetric stretching vibration peak of Fe-O-OH and is 1635cm-1Peak is SO4 2-A stretching vibration peak. Differently, due to Heat-FeS2The surface of (A) is partially oxidized by hot water vapor modification, so that Heat-FeS2in-OH, SO of the sample4 -2And the Fe-O-OH absorption peak intensity is obviously increased.
In addition, by the pair of FeS2/H2O2Active species analysis in the system shows that two active species OH and O for catalyzing and degrading alachlor2-Generated by the reaction of Heat-FeS2/H2O2And Fresh-FeS2/H2O2The OH concentration accumulated in the two systems is quantitatively calculated to find Heat-FeS2/H2O2The amount of OH produced per unit is about Fresh-FeS2/H2O24 times higher, indicating Heat-FeS2/H2O2The system can decompose H more quickly2O2Generation of OH, to H2O2Has higher utilization efficiency, which is Heat-FeS2/H2O2The root cause of the increase in catalytic activity of the system.
At the same time, we further speculate that Heat-FeS2/H2O2In the aerobic degradation process of alachlor in the system, the circulation mechanism of Fe (II)/Fe (III) is shown in figure 5. First, in a hot steam modification process, FeS2Fe on the surface of solid particles2+---FeS2And Fe3+---FeS2The content is greatly increased, and part of Fe3+---FeS2Is reduced toFe2+---FeS2And FeS on the surface2Forming a cycle; secondly, H is added2O2Then, Fe2+---FeS2First with H2O2Reaction to produce OH and form Fe3+---FeS2The generated OH can directly oxidize and mineralize alachlor to further generate low molecular by-products and a series of organic acids, and simultaneously, Fe3+---FeS2Adsorbing in FeS2Then reduced to Fe2+---FeS2Completing the second cycle; finally, Fe2+---FeS2And Fe3 +---FeS2Further dissociation in solution, Fe in solution2+And Fe3+The third cycle is again completed. This indicates that Heat-FeS2/H2O2The system has a plurality of Fe (II)/Fe (III) cycles, which not only can greatly increase Fe provided by Fenton reaction2 +---FeS2And Fe formed on the surface thereof2+---FeS2Can also be directly reacted with H2O2The reaction can quickly generate OH, so that H in the system is increased2O2The utilization rate of the alachlor is increased, more OH is generated, and the catalytic degradation of the alachlor is promoted. The above mechanism involves the following reactions:
FeS2+O2+H2O(g)→Fe2+---FeS2+2SO4 2-+2H+
Fe2+---FeS2+O2+H2O(g)→Fe3+---FeS2+O2 ·-+2H+
Fe3+---FeS2+FeS2+H2O(g)→Fe2+---FeS2+SO4 2-+H+
H2O2+Fe2+---FeS2→Fe3+---FeS2+·OH+-OH
O2+Fe2+---FeS2+H2O→Fe3+---FeS2+·O2 -+H+
Fe3+---FeS2+FeS2+H2O→Fe2+---FeS2+SO4 2-+H+
Fe2+---FeS2→Fe2++FeS2(S-L interface)
Fe3+---FeS2→Fe3++FeS2(S-L interface)
Fe2++H2O2→Fe3++·OH+-OH
Fe3++·O2 -→Fe2++O2
·OH+Alachlor→→→CO2+H2O
·O2 -+Alachlor→→→CO2+H2O
example 2
FeSO (ferric oxide) is added4.7H2O, sodium thiosulfate and sulfur powder are mixed and dissolved in 60mL of purified water according to the molar ratio of 1:1: 2. The mixture was stirred at room temperature for 0.5h, then hydrothermal at 190 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, washing and drying to obtain a sample of Fresh-FeS2. Then Fresh-FeS is added2Placing the sample in a watch glass, placing in a constant temperature water bath at 90 deg.C, and heating in water vapor atmosphere for 5 hr to obtain Heat-FeS sample2
Example 3
FeSO (ferric oxide) is added4.7H2O and Na2S is mixed and dissolved in 60mL of purified water in a molar ratio of 1: 4. The mixture was stirred at room temperature for 0.5h, then heated at 180 ℃ for 24 h. Naturally cooling to room temperature after the reaction is finished, washing and drying to obtain a sample of Fresh-FeS2. Then Fresh-FeS is added2Placing the sample in a watch glass, placing in a constant temperature water bath at 90 deg.C, and heating in water vapor atmosphere for 5 hr to obtain Heat-FeS sample2。
Example 4
Fresh-FeS2And Heat-FeS2Degrading alachlor:
weighing 50mgFreeh-FeS in example 12And Heat-FeS2Respectively adding 99.2mL of alachlor solution with the concentration of 20mg/L to the mixture, uniformly mixing the solution by oscillation, and respectively adding 0.8mL of H with the concentration of 100mM to the mixture2O2Placing the mixture in a magnetic stirrer, and setting the rotating speed to 700rpm for reaction; samples were taken from the flask at regular intervals using a syringe, filtered through a 0.22 μm filter and the Fenton reaction was stopped by adding 17.5mol/L glycerol stock solution, and the concentration of the remaining alachlor in the system was determined by high performance liquid chromatography.
While adding no H2O2The system of (5) and the blank experiment were compared, and the results are shown in FIG. 4, Freeh-FeS alone2The sample has about 5% of degradation rate to alachlor within 60 min; Fresh-FeS2/H2O2The degradation rate of the alachlor is not less than 30 percent within 60 min. However, Heat-FeS after the Hot Water steam modification treatment2/H2O2The degradation rate of the alachlor is close to 100 percent, and the degradation rate constant is (0.478 min)-1) Is unmodified Freeh-FeS2(0.021min-1) 23 times of the total amount of the modified FeS2The degradation efficiency is improved, which is beneficial to the rapid degradation of alachlor.
Claims (6)
1. A preparation method of a modified iron sulfide Fenton catalyst is characterized by comprising the following steps:
(1) weighing ferric salt and a sulfur source, placing the ferric salt and the sulfur source in a polytetrafluoroethylene tank, adding water, stirring, dissolving and uniformly mixing;
(2) heating to react, naturally cooling, washing and drying to obtain Fresh-FeS2；
(3) In the water vapor atmosphere, the obtained Fresh-FeS2Spreading and dispersing on a watch glass, and heating to obtain Heat-FeS2。
2. The method for preparing a modified iron sulfide-based fenton catalyst according to claim 1, wherein the sulfur source in step (1) is sodium sulfite, sodium sulfide, thiourea or ammonium sulfide.
3. Such as rightThe method for preparing a modified iron sulfide Fenton's catalyst according to claim 1, wherein the iron salt in the step (1) is FeSO4.7H2O; the molar ratio of the ferric salt to the sulfur source is 1 (1-4).
4. The method for preparing the modified iron sulfide Fenton catalyst according to claim 1, wherein sulfur powder is further added in the step (1), wherein the molar ratio of the iron salt, the sulfur source and the sulfur powder is 1:1 (1-3).
5. The method for preparing a modified iron sulfide Fenton's catalyst according to claim 1, wherein in the step (2), the temperature is raised to 140-200 ℃ for reaction for 24 hours.
6. The method for preparing a modified iron sulfide Fenton's catalyst according to claim 1, wherein the step (3) is performed by heating to 80-95 ℃ for 4-6 hours.
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| CN114314799A (en) * | 2021-12-31 | 2022-04-12 | 重庆大学 | Improved Fenton system and method for treating organic pollutants by utilizing same |
| CN114345372A (en) * | 2021-12-14 | 2022-04-15 | 广东环境保护工程职业学院 | Sulfur-containing compound and preparation method and application thereof |
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