CN112403495B - Layered mineral and iron polysulfide intercalation composite material and method and application thereof - Google Patents

Layered mineral and iron polysulfide intercalation composite material and method and application thereof Download PDF

Info

Publication number
CN112403495B
CN112403495B CN202011210957.0A CN202011210957A CN112403495B CN 112403495 B CN112403495 B CN 112403495B CN 202011210957 A CN202011210957 A CN 202011210957A CN 112403495 B CN112403495 B CN 112403495B
Authority
CN
China
Prior art keywords
mixture
iron
composite material
reducing agent
layered mineral
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011210957.0A
Other languages
Chinese (zh)
Other versions
CN112403495A (en
Inventor
陶春辉
艾曼青
叶瑛
杜昊
秦文莉
张楚青
陈雪刚
蔡巍
张平萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN202011210957.0A priority Critical patent/CN112403495B/en
Publication of CN112403495A publication Critical patent/CN112403495A/en
Application granted granted Critical
Publication of CN112403495B publication Critical patent/CN112403495B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • 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
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Abstract

The invention discloses a polysulfide intercalation composite material of layered mineral and iron, a method and application thereof. The preparation method comprises the following steps: putting ferric salt into a volatile organic solvent to obtain ferric salt compound solution; putting a reducing agent into water to prepare a reducing agent solution; mixing a layered mineral sample with an iron salt compound solution, and grinding in a grinder for 1-2 hours to obtain a mixture A; mixing the mixture A with a reducing agent solution, and grinding for 3-4 hours in a grinding machine to obtain a mixture B; calcining the mixture B under the protection of inert gas to obtain a mixture C; adding water, ethanol and CS to the mixture C in sequence2Stirring, cleaning and filtering to obtain a mixture D; and drying the mixture D and cooling to room temperature to obtain the composite material. The composite material can replace talc in the fields of microwave catalysis and functional coatings, has a far higher catalytic effect than other similar products, is low in cost and has higher chemical activity.

Description

Layered mineral and iron polysulfide intercalation composite material and method and application thereof
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a polysulfide intercalation composite material of layered minerals and iron, and a method and application thereof.
Background
After the talc is purified, the harmful impurities of the original talc are reduced, the use safety of the talc is improved, and the talc has wide application in material coatings and traditional Chinese medicines. However, talc has limited its use in catalysis due to its lower catalytic performance. The low-cost preparation technology and material composition are effective ways for expanding the application field of the talc material. The mineral materials are widely compounded, but the catalytic effect of the compounded mineral materials is low, and most of the mineral materials cannot meet the industrial requirements.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polysulfide intercalation composite material of layered minerals and iron, a method and application thereof.
The invention adopts the following specific technical scheme:
the first purpose of the invention is to provide a laminar mineral and iron polysulfide intercalation composite material, wherein iron polysulfide is inserted between crystal structure layers of the laminar mineral.
Preferably, the lamellar mineral is one of talc, vermiculite and montmorillonite.
The second purpose of the invention is to provide a preparation method of the polysulfide intercalation composite material of the lamellar mineral and iron, which comprises the following steps:
s1: putting ferric salt into a volatile organic solvent, and stirring until the ferric salt is completely dissolved to obtain a ferric salt compound solution;
s2: putting a reducing agent into water, and stirring until the reducing agent is completely dissolved to prepare a reducing agent solution;
s3: cleaning impurities on the surface of the layered mineral, drying, and cooling to room temperature to obtain a layered mineral sample;
s4: mixing a layered mineral sample with an iron salt compound solution, wherein the weight ratio of the layered mineral to the iron salt is 1: 0.2 to 0.5; after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A;
s5: mixing the mixture A with a reducing agent solution, wherein the weight ratio of the reducing agent to the ferric salt is 1: 0.5 to 1; after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B;
s6: calcining the mixture B under the protection of inert gas to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture C in sequence2Stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D;
s8: and drying the mixture D and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
Preferably, for the second purpose, the drying temperature is 60 to 80 ℃, and the mill is one of a ball mill, a roll mill, a rod mill and a bead mill.
Preferably, the volatile organic solvent is one of methanol, ethanol, propanol, isopropanol and ethylene glycol.
Preferably, for the second purpose, the iron salt is one of ferric chloride, ferrous sulfate, ferrous chloride, ferric fluoride, and ferric phosphate.
Preferably, the reducing agent is one of thiourea, sodium thiosulfate, sodium sulfide, sodium disulfide, and ammonium sulfide.
Preferably, in the step S6, the mixture B is placed in a tube furnace, and is calcined under the protection of nitrogen, and the temperature is kept constant at 200 ℃ for 12 hours, so that the mixture C is obtained.
Preferably, for the second purpose, in the step S7, water, ethanol and C are sequentially added to the mixture B in an amount of three to five times the volume of the mixture BS2Stirring for 2-4 hours, and then carrying out suction filtration and dehydration; the washing was repeated 3 times.
The third purpose of the present invention is to provide an application of the layered mineral and iron polysulfide intercalated composite material for catalytic degradation of persistent organic pollutants based on the first purpose of the present invention or the preferred mode thereof, wherein the mass concentration ratio of the persistent organic pollutants to the composite material is 4-50, and microwave catalytic degradation is performed.
Compared with the prior art, the invention has the following beneficial effects:
the preparation technology with low cost is characterized in that firstly, the mechanical-chemical force in the grinding process is utilized to insert the dissolved ferric salt into the crystal structure layer of the layered mineral, then the dissolved reducing agent is inserted into the crystal structure layer of the layered mineral, and the polysulfide of iron is reserved between layers by drying, so that the catalytic performance of the layered mineral is improved. The composite material prepared by the invention can replace original layered minerals in the fields of catalysis and functional coatings, remarkably improves the catalytic capability of the layered minerals on persistent organic pollutants, has a far higher catalytic effect than other similar products, is low in cost and has higher chemical activity.
Drawings
FIG. 1 is an X-ray diffraction pattern of talc (MT), iron polysulfide (FS) and composite material (TF);
FIG. 2 is a scanning electron micrograph in which (a) talc (MT), (b) iron polysulfide (FS), (c) and (d) are all composite materials (TF);
FIG. 3 is a spectrum of TF, wherein (a) the middle box is the point where the spectrum is taken and (b) the element content;
FIG. 4 is a transmission electron micrograph of MT and TF, wherein (a) and (b) are samples MT and (c) and (d) are samples TF;
in FIG. 5, (a) is a graph showing the change of the microwave catalytic degradation rate of the 2,4, 6-trichlorophenol standard solution with time by MT, FS, TF and a blank control group, and (b) is a full-spectrum scan of the TF on an ultraviolet spectrophotometer adsorbed by the 2,4, 6-trichlorophenol standard solution.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
The invention provides a laminar mineral and iron polysulfide intercalation composite material, which is formed by inserting iron polysulfide between crystal structure layers of laminar mineral, wherein the iron polysulfide refers to iron polysulfide FeSx. The layered mineral may be one of talc, vermiculite and montmorillonite, and the output form of the layered mineral in nature is clay, mudstone, shale or lump ore.
The preparation method of the composite material comprises the following steps:
s1: and (3) putting the ferric salt into a volatile organic solvent, and stirring until the ferric salt is completely dissolved to obtain a ferric salt compound solution. Wherein the volatile organic solvent can be one of methanol, ethanol, propanol, isopropanol and ethylene glycol, and the iron salt can be one of ferric chloride, ferrous sulfate, ferrous chloride, ferric fluoride and ferric phosphate.
S2: and (3) placing the reducing agent into deionized water, and stirring until the reducing agent is completely dissolved to obtain a reducing agent solution. Wherein the reducing agent can be one of thiourea, sodium thiosulfate, sodium sulfide, sodium disulfide and ammonium sulfide.
S3: adding water into the layered mineral for cleaning, then filtering or centrifugally dewatering, repeatedly cleaning for multiple times to remove surface impurities of the layered mineral, then drying at the temperature of 60-80 ℃, and cooling to room temperature to obtain a layered mineral sample.
S4: mixing the cooled layered mineral sample with an iron salt compound solution, wherein the weight ratio of the layered mineral to the iron salt is 1: 0.2 to 0.5. And after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: mixing the mixture A with a reducing agent solution, wherein the weight ratio of the reducing agent to the ferric salt is 1: 0.5 to 1. And after uniformly stirring, continuously grinding for 3-4 hours in a grinding machine to obtain a mixture B. Wherein the grinder may be one of a ball mill, a roll mill, a rod mill and a bead mill.
S6: adding water, ethanol and CS into the mixture B in sequence, wherein the volume of the water, the ethanol and the CS is three to five times that of the mixture B2And stirring for 2-4 hours, and then carrying out suction filtration and dehydration. The washing was repeated 3 times to remove impurities (such as sulfur, iron salts, reducing agents, etc.) from the mixture B to obtain a mixture C.
S7: and drying the mixture C at the temperature of 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
The polysulfide intercalation composite material of the layered mineral and the iron can effectively catalyze and degrade persistent organic pollutants by microwaves, wherein the mass concentration ratio of the persistent organic pollutants to the composite material is 4-50.
The preparation technology with low cost is characterized in that firstly, the mechanical-chemical force in the grinding process is utilized to insert the dissolved ferric salt into the crystal structure layer of the layered mineral, then the dissolved reducing agent is inserted into the crystal structure layer of the layered mineral, and the polysulfide of iron is reserved between layers by drying, so that the catalytic performance of the layered mineral is improved. The composite material prepared by the invention can replace original layered minerals in the fields of catalysis and functional coatings, remarkably improves the catalytic capability of the layered minerals on persistent organic pollutants, has a far higher catalytic effect than other similar products, is low in cost and has higher chemical activity.
Example 1
S1: putting ferric chloride hexahydrate into absolute ethyl alcohol, and stirring until the ferric chloride hexahydrate is completely dissolved to obtain a ferric chloride solution.
S2: and (3) placing the sodium sulfide into deionized water, and stirring until the sodium sulfide is completely dissolved to obtain a sodium sulfide solution.
S3: and (3) taking talc which is 3 times of the weight of ferric chloride hexahydrate in S1, cleaning surface impurities of the talc, drying the talc at 60 ℃, and cooling the talc to room temperature to obtain a talc sample.
S4: mixing a talc sample with an iron chloride solution, wherein the mixing weight ratio of the talc to the iron chloride is 1: 0.2. And after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: mixing the mixture A with a sodium sulfide solution, wherein the weight ratio of sodium sulfide to ferric chloride hexahydrate is 1: 0.5. and after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B.
S6: placing the mixture B in a tube furnace, calcining under the protection of nitrogen, and keeping the temperature at 200 ℃ for 12 hours to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture B in sequence2And stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D.
S8: and drying the mixture D at 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
Example 2
S1: and (3) placing anhydrous ferric chloride into anhydrous ethanol, and stirring until the anhydrous ferric chloride is completely dissolved to obtain a ferric chloride solution.
S2: and (3) putting the sodium thiosulfate into deionized water, and stirring until the sodium thiosulfate is completely dissolved to obtain a sodium thiosulfate solution.
S3: and (3) taking talc which is 3 times the weight of the anhydrous ferric chloride in the S1, cleaning surface impurities of the talc, drying the talc at 60 ℃, and cooling the talc to room temperature to obtain a talc sample.
S4: mixing a talc sample with an iron chloride solution, wherein the mixing weight ratio of the talc to the iron chloride is 1: 0.2. And after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: and mixing the mixture A with a sodium thiosulfate solution, wherein the weight ratio of the sodium thiosulfate to the anhydrous ferric chloride is 1: 1. and after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B.
S6: placing the mixture B in a tube furnace, calcining under the protection of nitrogen, and keeping the temperature at 200 ℃ for 12 hours to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture C in sequence2And stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D.
S8: and drying the mixture D at 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
Example 3
S1: and (3) putting the ferric fluoride into absolute ethyl alcohol, and stirring until the ferric fluoride is completely dissolved to obtain a ferric fluoride solution.
S2: and (3) putting the sodium thiosulfate into deionized water, and stirring until the sodium thiosulfate is completely dissolved to obtain a sodium thiosulfate solution.
S3: and (3) taking talc which is 3 times of the weight of the ferric fluoride in the S1, cleaning surface impurities of the talc, drying the talc at 60 ℃, and cooling the talc to room temperature to obtain a talc sample.
S4: mixing a talc sample with an iron fluoride solution, wherein the mixing weight ratio of the talc to the iron fluoride is 1: 0.4. And after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: and mixing the mixture A with a sodium thiosulfate solution, wherein the weight ratio of the sodium thiosulfate to the ferric fluoride is 1: 1. and after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B.
S6: placing the mixture B in a tube furnace, calcining under the protection of nitrogen, and keeping the temperature at 200 ℃ for 12 hours to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture C in sequence2And stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D.
S8: and drying the mixture D at 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
The composite material is used for carrying out a catalytic degradation test on phenol according to the following modes:
1) dissolving phenol in deionized water, and fixing the volume to prepare a phenol stock solution with the concentration of 500 mg/L.
2) 1 part of phenol stock solution is added with 5 times of deionized water to prepare a phenol standard solution with the concentration of 50 mg/L.
3) And putting the prepared composite material into a phenol standard solution, and performing microwave catalytic degradation.
4) And (4) carrying out centrifugal separation on the solution after catalytic degradation to finish the catalytic degradation process of the phenol.
Example 4
S1: putting ferric chloride hexahydrate into absolute ethyl alcohol, and stirring until the ferric chloride hexahydrate is completely dissolved to obtain a ferric chloride hexahydrate solution.
S2: and (3) putting thiourea into deionized water, and stirring until the thiourea is completely dissolved to obtain a thiourea solution.
S3: and (3) taking talc which is 3 times of the weight of ferric chloride hexahydrate in S1, cleaning surface impurities of the talc, drying the talc at 60 ℃, and cooling the talc to room temperature to obtain a talc sample.
S4: mixing a talc sample with a ferric chloride hexahydrate solution, wherein the mixing weight ratio of the talc to the ferric chloride hexahydrate is 1: 0.5. and after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: and mixing the mixture A with a thiourea solution, wherein the weight ratio of thiourea to ferric chloride hexahydrate is 1: 0.8. And after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B.
S6: ferric chloride hexahydrate with thiourea 5: 8, stirring for 6 hours, drying, and calcining at 200 ℃ for 12 hours under the protection of nitrogen to obtain the polysulfide FS of iron.
S7: placing the mixture B in a tube furnace, calcining under the protection of nitrogen, and keeping the temperature at 200 ℃ for 12 hours to obtain a mixture C;
s8: adding water, ethanol and CS to the mixture C in sequence2And stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D.
S9: and drying the mixture D at 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
The composite material is used for carrying out a catalytic degradation test on 2,4, 6-trichlorophenol according to the following mode:
1) dissolving 2,4, 6-trichlorophenol in deionized water, and diluting to a constant volume to obtain a 2,4, 6-trichlorophenol stock solution with the concentration of 500 mg/L.
2) 1 part of 2,4, 6-trichlorophenol stock solution is added with 5 times of deionized water to prepare a 2,4, 6-trichlorophenol standard solution with the concentration of 50 mg/L.
3) And putting the prepared composite material into a 2,4, 6-trichlorophenol standard solution, and performing microwave catalytic degradation.
4) And (4) carrying out centrifugal separation on the solution after catalytic degradation to finish the catalytic degradation process of the 2,4, 6-trichlorophenol.
Example 5
S1: and (3) placing anhydrous ferric chloride into anhydrous ethanol, and stirring until ferric fluoride is completely dissolved to obtain an anhydrous ferric chloride solution.
S2: and (3) placing the sodium disulfide into deionized water, and stirring until the sodium disulfide is completely dissolved to obtain a sodium disulfide solution.
S3: and (3) taking talc which is 3 times the weight of the anhydrous ferric chloride in the S1, cleaning surface impurities of the talc, drying the talc at 60 ℃, and cooling the talc to room temperature to obtain a talc sample.
S4: mixing a talc sample with an anhydrous ferric chloride solution, wherein the mixing weight ratio of the talc to the anhydrous ferric chloride is 1: 0.7. and after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A.
S5: mixing the mixture A with a sodium disulfide solution, wherein the weight ratio of sodium disulfide to anhydrous ferric chloride is 1: 0.9. and after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B.
S6: placing the mixture B in a tube furnace, calcining under the protection of nitrogen, and keeping the temperature at 200 ℃ for 12 hours to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture C in sequence2And stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D.
S8: and drying the mixture D at 60-80 ℃ and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
The composite material is used for carrying out a catalytic degradation test on the 2, 4-dichlorophenol according to the following mode:
1) dissolving 2, 4-dichlorophenol in deionized water, and fixing the volume to obtain a 2, 4-dichlorophenol stock solution with the concentration of 500 mg/L.
2) And adding 5 times of deionized water into 1 part of 2, 4-dichlorophenol stock solution to prepare a 2, 4-dichlorophenol standard solution with the concentration of 50 mg/L.
3) And putting the prepared composite material into a 2, 4-dichlorophenol standard solution, and performing microwave catalytic degradation.
4) And (4) carrying out centrifugal separation on the solution after catalytic degradation to finish the catalytic degradation process of the 2, 4-dichlorophenol.
In each of examples 1 to 5, a polysulfide intercalation composite material of a layered mineral and iron can be prepared, and the iron polysulfide can be stably inserted into the crystal structure layer of the layered mineral by characterization. In examples 3 to 5, the solution after microwave catalysis is subjected to corresponding content measurement of the catalytically degraded substance, i.e., the catalytic removal rate can be calculated to characterize the catalytic degradation performance of the prepared composite material. The results show that the composite materials prepared in the examples 3 to 5 have good catalytic degradation performance on corresponding persistent organic pollutants.
The following discussion of structural characterization and catalytic degradation effects of the composite material prepared in example 4 is provided, with the following results:
composite material characterization:
FIG. 1 is an X-ray diffraction pattern of talc (MT), iron polysulfide (FS) and composite material (TF). From the data in fig. 1, it can be found that: FS at 27.77 °, 32.95 ° and 36.97 ° 2 θ, presents #71-0053FeS2Is characterized by a diffraction peak corresponding to a layer interval of d(111)＝3.21nm、d(200)＝2.72 nm、d(210)2.43 nm. In addition, the characteristic diffraction peak of #76-0964FeS is at d(111)The results show that the iron polysulfides produced are mainly FeS and FeS, as evidenced by the appearance at 3.86nm and 2 θ of 23.04 °2。
TF characteristic diffraction peaks of MT appear at 9.4 °, 18.68 ° and 25.03 ° 2 θ, with corresponding layer spacings d(001)0.94nm, 0.47nm, and 0.355 nm. The overall peak intensity of TF is reduced relative to the peak of the MT stone, possibly due to defects in the MT lattice caused by FS insertion. After FS is inserted between the composite layers, TF is 2 theta ═The decrease in the grain size from 1.01 to 0.41 indicates that the (001) peak is shifted to the left, resulting in a larger interlayer distance, from a peak strength at 6.20 ° to a peak strength at (001) which is increased from 0.39 to 0.71 before intercalation. Wherein sample TF exhibited characteristic diffraction peaks of #76-0964FeS (111) and #76-093FeS (200) at 2 θ 23.04 ° and 25.82 °, and exhibited characteristic diffraction peaks of #71-0053FeS at 2 θ 27.69 °2The characteristic diffraction peak of (111).
Additionally, under the influence of MT and FS lattices, the characteristic diffraction peak of MT at 29.38 ° for TF disappears, while the relative peak intensities at 34.73 °, 35.30 ° and 36.84 ° for TF (in contrast to the peak intensity of (001) for MT) increase from 0.10, 0.19 and 0.13 to 0.23, 0.40 and 0.27, respectively.
It can be seen that the intercalated composite of layered mineral and iron polysulfide is a composite formed by inserting iron polysulfide between mineral crystal structure layers, and the interlayer spacing of XRD becomes larger, which proves that the iron polysulfide is inserted between layered mineral crystal structure layers, rather than simple surface modification.
FIG. 2 shows scanning electron micrographs of all samples (MT, FS and TF). The MT shown in FIG. 2(a) is a clear sheet-like structure. As can be seen from FIG. 2(b), FS has an irregular block or spherical structure and has significant agglomeration. FIGS. 2(c) and (d) both show the results of scanning electron microscopy of TF, from which it was found that TF exhibits a clear sheet-like structure accompanied by a very small amount of needle-like structure.
The spectral results in FIG. 3 show that iron (Fe) and sulfur (S) are present in TF and that the specific gravities are 3.3% and 0.81%, respectively. The above results show that iron polysulfides have been inserted between the structural layers of talc lamellae.
FIG. 4 is a transmission electron micrograph. Wherein, the picture a is the transmission electron microscope picture of MT, and the MT can be known to have a clear and clean sheet structure through the picture. And TF is a b diagram, and clear and dense block structures exist among layers. In combination with SEM images of TF, it can be seen that there is a certain amount of FS inside the relatively clean surface.
In view of the above, it can be judged that iron polysulfide has been inserted into the surface of the crystal structure layer between the layers of talc, i.e., the layered mineral and iron polysulfide intercalated composite material has been successfully prepared.
(II) microwave catalytic degradation effect
From the results in fig. 5, it can be seen that in the case of not adding any catalyst (i.e. Blank control group Blank), the microwave itself has a certain degradation effect on the pollutant, and 11.79% of the pollutant can be degraded after 5 min. The MT is shifted due to the characteristic peak value (294nm) of the pollutant, so that the peak value at 294nm is increased, which indicates that the talc has no degradation effect on the pollutant and prevents the degradation of the pollutant by microwave due to the special chemical property of the talc. FS only degraded 51.87% of the contaminants after 5 min. TF can degrade 94.21% of pollutants to reach balance after 4min while maintaining the optimal degradation effect. FIG. 5(b) shows a full spectrum scan of TF with respect to the UV spectrophotometer adsorbed by the 2,4, 6-trichlorophenol standard solution. As can be seen from the graph, the characteristic peak of 2,4, 6-trichlorophenol at 293nm disappeared after 4 minutes, and the full spectrum result is close to a straight line. The results prove that the composite material can obviously improve the catalytic degradation efficiency of 2,4, 6-trichlorophenol.
TABLE 1 COD content in solution before and after catalytic degradation
COD value (mg/L) Standard deviation (mg/L) COD removal rate% Standard deviation of%
Stock solution 66.20 1.77 —— ——
Blank sample 54.38 2.89 17.85 4.37
TF 6.52 0.71 90.15 1.07
Table 1 shows the COD content of the solution before and after catalytic degradation. After the microwave catalysis is carried out on the blank sample, the COD content of the blank sample is reduced from 60.20mg/L to 54.38mg/L, which shows that the microwave catalysis has a certain mineralization effect on the 2,4, 6-trichlorophenol. After the sample TF was added, the COD content of the solution was reduced to 6.5 mg/L. The results show that the polysulfide intercalation composite material of the layered minerals and the iron can completely mineralize the 2,4, 6-trichlorophenol, and the secondary pollution condition does not exist.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.

Claims (6)

1. The application of polysulfide intercalation composite material based on layered minerals and iron for catalytic degradation of persistent organic pollutants is characterized in that the mass concentration ratio of the persistent organic pollutants to the composite material is 4-50, and microwave is adopted for catalytic degradation;
the composite material is a polysulfide of iron inserted between crystal structure layers of layered minerals, and the preparation method comprises the following steps:
s1: putting ferric salt into a volatile organic solvent, and stirring until the ferric salt is completely dissolved to obtain a ferric salt compound solution; the ferric salt is one of ferric chloride, ferrous sulfate, ferrous chloride, ferric fluoride and ferric phosphate;
s2: putting a reducing agent into water, and stirring until the reducing agent is completely dissolved to prepare a reducing agent solution; the reducing agent is one of thiourea, sodium thiosulfate, sodium sulfide, sodium disulfide and ammonium sulfide;
s3: cleaning impurities on the surface of the layered mineral, drying, and cooling to room temperature to obtain a layered mineral sample;
s4: mixing a layered mineral sample with an iron salt compound solution, wherein the weight ratio of the layered mineral to the iron salt is 1: 0.2 to 0.5; after uniformly stirring, grinding in a grinding machine for 1-2 h to obtain a mixture A;
s5: mixing the mixture A with a reducing agent solution, wherein the weight ratio of the reducing agent to the ferric salt is 1: 0.5 to 1; after uniformly stirring, grinding in a grinding machine for 3-4 h to obtain a mixture B;
s6: calcining the mixture B under the protection of inert gas to obtain a mixture C;
s7: adding water, ethanol and CS to the mixture C in sequence2Stirring, cleaning and filtering to remove impurities in the mixture C to obtain a mixture D;
s8: and drying the mixture D and cooling to room temperature to obtain the polysulfide intercalation composite material of the layered mineral and the iron.
2. The use according to claim 1, wherein the layered mineral is one of talc, vermiculite and montmorillonite.
3. The use of claim 1, wherein the drying temperature is 60-80 ℃, and the mill is one of a ball mill, a roller mill, a rod mill and a bead mill.
4. Use according to claim 1, wherein the volatile organic solvent is one of methanol, ethanol, propanol, isopropanol and ethylene glycol.
5. The use according to claim 1, wherein in S6, mixture B is placed in a tube furnace, and is calcined under the protection of nitrogen gas, and the temperature is kept constant at 200 ℃ for 12h to obtain mixture C.
6. The use of claim 1, wherein in S7, water, ethanol and CS are sequentially added to mixture B in a volume three to five times that of mixture B2Stirring for 2-4 hours, and then carrying out suction filtration and dehydration; the washing was repeated 3 times.
CN202011210957.0A 2020-11-03 2020-11-03 Layered mineral and iron polysulfide intercalation composite material and method and application thereof Active CN112403495B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011210957.0A CN112403495B (en) 2020-11-03 2020-11-03 Layered mineral and iron polysulfide intercalation composite material and method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011210957.0A CN112403495B (en) 2020-11-03 2020-11-03 Layered mineral and iron polysulfide intercalation composite material and method and application thereof

Publications (2)

Publication Number Publication Date
CN112403495A CN112403495A (en) 2021-02-26
CN112403495B true CN112403495B (en) 2022-04-01

Family

ID=74827410

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011210957.0A Active CN112403495B (en) 2020-11-03 2020-11-03 Layered mineral and iron polysulfide intercalation composite material and method and application thereof

Country Status (1)

Country Link
CN (1) CN112403495B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101707216B (en) * 2009-11-30 2011-03-23 北京化工大学 Hydrotalcite based solar energy photoelectric thin-film material and method for preparing same
CN102344194B (en) * 2011-06-14 2013-01-02 中国科学院新疆理化技术研究所 Method for preparing montmorillonite in situ intercalation type nanoscale zero-valent iron
CN102923835B (en) * 2012-11-09 2014-10-15 中国科学技术大学 Nano zero-valent iron with montmorillonite serving as carrier, and preparation method and application thereof
CN104058467B (en) * 2014-07-06 2016-02-24 浙江大学 A kind of layer mineral and nanometer iron carbonyl intercalation composite material and preparation method thereof
CN104291435B (en) * 2014-11-03 2016-04-20 济南大学 A kind of method of Fe/FeS matrix material activate molecular oxygen process organic waste water
CN110420648B (en) * 2019-07-12 2022-05-10 华南师范大学 Iron-sulfur coupling catalyst capable of efficiently degrading high-concentration phenol and preparation method and application thereof
CN110252343A (en) * 2019-07-15 2019-09-20 南京师范大学 A kind of FeS-GQDs composite nano materials and its preparation method and application
CN110451516A (en) * 2019-09-03 2019-11-15 浙江大学 Layer mineral and quaternary ammonium salt surface active agent intercalation composite material and preparation method

Also Published As

Publication number Publication date
CN112403495A (en) 2021-02-26

Similar Documents

Publication Publication Date Title
Guo et al. 2D/2D Z-scheme heterojunction of CuInS2/g-C3N4 for enhanced visible-light-driven photocatalytic activity towards the degradation of tetracycline
Abraham et al. Enhanced magneto-optical and photo-catalytic properties of transition metal cobalt (Co2+ ions) doped spinel MgFe2O4 ferrite nanocomposites
Abd Elkodous et al. Nanocomposite matrix conjugated with carbon nanomaterials for photocatalytic wastewater treatment
Abu-Dief et al. Facile synthesis and characterization of novel Gd2O3–CdO binary mixed oxide nanocomposites of highly photocatalytic activity for wastewater remediation under solar illumination
Wu et al. In-situ synthesis of novel pn heterojunction of Ag2CrO4-Bi2Sn2O7 hybrids for visible-light-driven photocatalysis
Shi et al. Fabrication of MoS 2/BiOBr heterojunctions on carbon fibers as a weaveable photocatalyst for tetracycline hydrochloride degradation and Cr (VI) reduction under visible light
Zhou et al. One-step synthesis of Ceria/Ti3C2 nanocomposites with enhanced photocatalytic activity
Cao et al. A novel CdWO4/BiOBr p–n heterojunction as visible light photocatalyst
Xu et al. Monodispersed Ag 3 PO 4 nanocrystals loaded on the surface of spherical Bi 2 MoO 6 with enhanced photocatalytic performance
Xu et al. Fabrication of Mn/O co-doped g-C3N4: excellent charge separation and transfer for enhancing photocatalytic activity under visible light irradiation
Chai et al. In-situ construction of Bi2SiO5/BiOBr heterojunction with significantly improved photocatalytic activity under visible light
Rajavel et al. Photocatalytic and bactericidal properties of MXene-derived graphitic carbon-supported TiO2 nanoparticles
Guo et al. Sol-gel synthesis of new ZnFe2O4/Na-bentonite composites for simultaneous oxidation of RhB and reduction of Cr (VI) under visible light irradiation
Wu et al. Solvothermal fabrication of La-WO3/SrTiO3 heterojunction with high photocatalytic performance under visible light irradiation
Cai et al. Oxygen vacancies enriched BiOBr with boosted photocatalytic behaviors
Chahal et al. Erbium-doped oxygen deficient cerium oxide: bi-functional material in the field of spintronics and photocatalysis
Wu The fabrication of magnetic recyclable nitrogen modified titanium dioxide/strontium ferrite/diatomite heterojunction nanocomposite for enhanced visible-light-driven photodegradation of tetracycline
Alijani et al. Efficient photocatalytic degradation of toxic dyes over BiFeO3/CdS/rGO nanocomposite under visible light irradiation
Nie et al. Highly efficient removal of Cr (VI) by hexapod-like pyrite nanosheet clusters
Yang et al. A {110} facet predominated Bi 6 O 6 (OH) 3 (NO 3) 3· 1.5 H 2 O photocatalyst: selective hydrothermal synthesis and its superior photocatalytic activity for degradation of phenol
Wu et al. Defective BiO2-x/BiOCl porous ultrathin nanosheets for efficient solar-light-driven photoreduction of Cr (VI)
CN107774283B (en) Molybdenum disulfide intercalated hydrotalcite composite material and preparation method and application thereof
Yan et al. Evenly distribution of amorphous iron sulfides on reconstructed Mg-Al hydrotalcites for improving Cr (VI) removal efficiency
Cao et al. Effect of chemisorbed surface species on the photocatalytic activity of TiO2 nanoparticulate films
CN112403495B (en) Layered mineral and iron polysulfide intercalation composite material and method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant