CN114212831B - Cobalt-modified zero-valent iron sulfide and preparation method and application thereof - Google Patents
Cobalt-modified zero-valent iron sulfide and preparation method and application thereof Download PDFInfo
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- CN114212831B CN114212831B CN202110702053.8A CN202110702053A CN114212831B CN 114212831 B CN114212831 B CN 114212831B CN 202110702053 A CN202110702053 A CN 202110702053A CN 114212831 B CN114212831 B CN 114212831B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 16
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000000987 azo dye Substances 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 abstract description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 210000002966 serum Anatomy 0.000 description 76
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 28
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 26
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 20
- 238000007885 magnetic separation Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 11
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 4
- 230000010757 Reduction Activity Effects 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
Classifications
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- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/306—Pesticides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses cobalt-modified zero-valent iron sulfide, and a preparation method and application thereof, wherein the preparation method comprises the following steps: and under the normal temperature condition, adding the zero-valent iron sulfide into a soluble cobalt salt aqueous solution for reaction, and separating to obtain the cobalt-modified zero-valent iron sulfide material. According to the invention, the zero-valent iron sulfide is added into the soluble cobalt salt aqueous solution, cobalt ions are used for replacing FeS on the surface of the zero-valent iron sulfide to form a CoS-containing material, so that pollutants which can be degraded by conventional zero-valent iron sulfide can be effectively degraded, and the problem that the 1, 2-dichloroethane and cis-1, 2-dichloroethylene are difficult to degrade by the zero-valent iron sulfide can be solved.
Description
Technical Field
The invention relates to the technical field of environmental chemistry, in particular to cobalt-modified zero-valent iron sulfide, and a preparation method and application thereof.
Background
Zero-valent iron is a very common substance in our life, and is widely applied to degrading and removing organic pollutants and inorganic pollutants in the environment due to active chemical properties, abundant sources, low price, great electronegativity and strong reducibility. The discovery of nano zero-valent iron has brought a wider space for the development of zero-valent iron since the 21 st century.
Although the nano zero-valent iron has the characteristics of excellent reaction activity, low cost and low toxicity, the nano zero-valent iron also faces the limitation of storage, long-acting property and the like due to the self property. In a modification method for improving the practical application potential of nano zero-valent iron in water environment, vulcanization becomes a research hot spot in recent years. The vulcanized zero-valent iron is a modified material which is formed by doping sulfur on the surface of the zero-valent iron to form a sulfide on the surface of the zero-valent iron. The sulfidic zero-valent iron is a modification revolution which is raised in recent years, and the research focus of modification is transferred from the improvement of the reactivity of the zero-valent iron to the improvement of the electron selectivity. Sulfide on the surface of the vulcanized zero-valent iron makes electron transfer more prone to pollutants rather than water molecules, and meanwhile passivation of materials is restrained, so that service life and degradation capacity of the zero-valent iron are greatly improved.
The zero valent iron sulfide can be prepared by sodium borohydride reduction (CN 104492461A), mechanical ball milling (Gu, Y.; wang, B.; he, F.; bradley, M.J.; tratnylek, P.G.mechanochemical sulfidated microscale zero valent iron: pathwalys, kinetics, mechanism, and efficiency of trichloroethylene dechlorination, environ. Sci. Technology 2017,51 (21), 12653-12662.; and elemental sulfur aqueous phase sulfidation (201811634376.2), among others. The research shows that the vulcanization methods can obviously improve the rate of zero-valent iron for removing halogenated organics such as trichloroethylene, chloroform, carbon tetrachloride, tetrachloroethylene and the like, but the halogenated organics such as 1, 2-dichloroethane, cis-1, 2-dichloroethylene and the like are difficult to remove.
Therefore, it is necessary to further explore the modification treatment of zero-valent iron sulfide to further improve the reduction activity of the material and realize the rapid removal of halogenated organics such as trichloroethylene, 1, 2-dichloroethane and cis-1, 2-dichloroethylene.
Disclosure of Invention
The invention provides cobalt-modified zero-valent iron sulfide, a preparation method and application thereof, wherein the preparation method has the advantages of easy raw material acquisition, less energy consumption, simple and convenient operation and low preparation cost, and the prepared cobalt-modified zero-valent iron sulfide solves the difficult problems of difficult degradation of the zero-valent iron sulfide of 1, 2-dichloroethane and cis-1, 2-dichloroethylene.
The specific technical scheme is as follows:
a method for preparing cobalt-modified zero-valent iron sulfide, comprising: and under the normal temperature condition, adding the zero-valent iron sulfide into a soluble cobalt salt aqueous solution for reaction, and separating to obtain the cobalt-modified zero-valent iron sulfide material.
The solubility of CoS is obviously lower than that of FeS, so that bivalent cobalt ions can replace bivalent iron ions in FeS, and a layer of CoS is formed on the surface of the zero-valent iron sulfide, so that the cobalt-modified zero-valent iron sulfide is prepared; experiments show that the cobalt-modified zero-valent iron sulfide can degrade pollutants degraded by conventional zero-valent iron sulfide more quickly, and can further degrade other pollutants difficult to degrade the zero-valent iron sulfide, namely: 1, 2-dichloroethane and cis-1, 2-dichloroethylene.
The normal temperature refers to the natural environment temperature, and the temperature range is 15-25 ℃ without manual regulation.
Preferably, the conditions are an anaerobic environment, i.e.: the system is in an environment with low oxygen content, so that the loss of zero-valent iron caused by the consumption of the material by oxygen can be effectively avoided.
The zero-valent iron sulfide can be nanoscale zero-valent iron sulfide or micron-order zero-valent iron sulfide, and the type and the size range of the zero-valent iron sulfide are not limited.
The zero-valent iron sulfide can be prepared by a sodium borohydride reduction method, a mechanical ball milling method and a simple substance sulfur aqueous phase synthesis method, the preparation method is not limited, and the size range of the zero-valent iron sulfide is not limited.
Further, the molar ratio of the sulfur element to the iron element in the zero-valent iron sulfide is 0.01-0.8:1; the addition amount of cobalt ions in the cobalt salt aqueous solution is 1-100 percent based on the molar consumption of sulfur element. Preferably, the molar ratio of the sulfur element to the iron element in the zero-valent iron sulfide is 0.05-0.8:1; the addition amount of cobalt ions in the cobalt salt aqueous solution is 3% -100% based on the molar consumption of sulfur element; more preferably, the molar ratio of the sulfur element to the iron element in the zero-valent iron sulfide is 0.05-0.2:1; the addition amount of cobalt ions in the cobalt salt aqueous solution is 60-100 percent based on the molar consumption of sulfur element.
Preferably, the invention provides a preparation method of zero-valent iron sulfide, which comprises the following steps: under the normal temperature condition, adding elemental sulfur powder and zero-valent iron into an aqueous solution for mixed reaction to prepare vulcanized zero-valent iron; the aqueous solution is an acidic aqueous solution, an inorganic salt solution or a pH buffer solution.
Further, the ratio of the amount of the elemental sulfur powder to the amount of the zero-valent iron substance is 0.01-0.8:1.
Further, the solute of the dilute acid solution is HCl; the inorganic salt is MgCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The pH buffer solution is morpholinoethanesulfonic acid solution.
Preferably, the invention also provides another preparation method of the vulcanized zero-valent iron, namely: ball milling elemental sulfur powder and zero-valent iron at normal temperature to obtain vulcanized zero-valent iron; the mol ratio of the elemental sulfur powder to the zero-valent iron is 0.05-0.2:1.
Furthermore, the invention only needs to ensure that the cobalt salt aqueous solution is soluble salt, and does not strictly limit what cobalt salt is. Preferably, the soluble cobalt salt is CoCl 2 。
Further, the reaction time is > 30min.
The invention also provides cobalt-modified zero-valent iron sulfide prepared by the preparation method.
The invention also provides application of the cobalt-modified zero-valent iron sulfide in treating halogenated organic species, heavy metals, pesticides, azo dyes and/or nitroorganic species polluted water.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the zero-valent iron sulfide is added into the soluble cobalt salt aqueous solution, cobalt ions are used for replacing FeS on the surface of the zero-valent iron sulfide to form a CoS-containing material, so that pollutants which can be degraded by conventional zero-valent iron sulfide can be effectively degraded, and the problem that the 1, 2-dichloroethane and cis-1, 2-dichloroethylene are difficult to degrade by the zero-valent iron sulfide can be solved.
Drawings
FIG. 1 is an EDS diagram of cobalt-modified zero-valent iron sulfide produced in example 1.
FIG. 2 is an XPS plot of cobalt-modified zero valent iron sulfide produced in example 1.
FIG. 3 is a graph showing the effect of the materials prepared in example 1, example 2, example 3 and comparative example 1 in application example 1 on removal of Trichloroethylene (TCE).
FIG. 4 is a graph showing the effect of the materials prepared in example 4 and comparative example 2 of application example 1 on removal of Trichloroethylene (TCE).
FIG. 5 is a graph showing the effect of the materials prepared in example 5 and comparative example 3 of application example 1 on removal of Trichloroethylene (TCE).
FIG. 6 is a graph showing the effect of the materials prepared in example 6 and comparative example 4 of application example 1 on removal of Trichloroethylene (TCE).
FIG. 7 is a graph showing the product distribution of Trichloroethylene (TCE) degraded by the materials prepared in example 1 and comparative example 1 of application example 1.
Detailed Description
The invention will be further described with reference to the following examples, which are given by way of illustration only, but the scope of the invention is not limited thereto.
The main raw materials such as zero-valent iron, elemental sulfur powder, cobalt chloride and the like in the following examples are all from Allatin (Shanghai, china), and all reagents are analytically pure, wherein the particle size of the zero-valent iron is 38 mu m, and the particle size of the elemental sulfur powder is 40 mu m.
Example 1
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of morpholinoethanesulfonic acid (MES) solution at an initial pH of 6, 50mM was added to the serum bottle under anaerobic conditions. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; after washing zero-valent iron sulfide three times by using anaerobic water, adding 26mL of cobalt chloride solution with the concentration of 10mM (the content of cobalt ions is 60% of that of sulfur element) into a serum bottle, and continuously placing the mixture into a rotary mixer for rotary mixing reaction for 1h to obtain cobalt-modified zero-valent iron sulfide; finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Fig. 1 is an EDS diagram of cobalt-modified zero-valent iron sulfide prepared in this example, from which it is known that cobalt element is present on the material, and the cobalt element accounts for 1.6%, which indicates that the present invention can successfully load cobalt element onto zero-valent iron sulfide to obtain a cobalt-modified zero-valent iron sulfide material. Fig. 2 is an XPS diagram of cobalt-modified zero-valent iron sulfide obtained in this example, and the result also demonstrates that cobalt element is successfully loaded onto the zero-valent iron sulfide, and that cobalt element on the surface of the zero-valent iron sulfide exists in various forms, including cobalt sulfide morphology.
Example 2
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of morpholinoethanesulfonic acid (MES) solution at an initial pH of 6, 50mM was added to the serum bottle under anaerobic conditions. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times with oxygen-free water, 26mL of a cobalt chloride solution with a concentration of 1mM (the amount of cobalt ions is 6% of that of sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer to be subjected to rotary mixing reaction for 1h, so that cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 3
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of morpholinoethanesulfonic acid (MES) solution at an initial pH of 6, 50mM was added to the serum bottle under anaerobic conditions. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times by using oxygen-free water, 26mL of cobalt chloride solution with the concentration of 0.5mM (the content of cobalt ions is 3 percent of the sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer for rotary mixing reaction for 1 hour, so that the cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 4
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). Under anaerobic condition, adding into serum bottle26mL of MgCl with an initial pH of 6.5 and 10mM 2 A solution. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times by using oxygen-free water, 26mL of cobalt chloride solution with the concentration of 0.5mM (the content of cobalt ions is 3 percent of the sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer for rotary mixing reaction for 1 hour, so that the cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 5
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of HCl solution with an initial pH of 4 and 0.1mM were added to the serum bottle under anaerobic conditions. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 48 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times by using oxygen-free water, 26mL of a 17mM cobalt chloride solution (the amount of cobalt ions is 100% of that of sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer to be subjected to rotary mixing reaction for 1h, so that cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 6
Taking 0.125g of elemental sulfur powder and 2.365g of zero-valent iron in a 100mL stainless steel ball milling tank (the ratio of the sulfur powder to the zero-valent iron is 0.1), adding 50 zirconia ball milling beads (the particle size is 6 mm), filling argon into the ball milling tank as shielding gas, sealing, placing the ball milling tank on a planet ball mill, starting the ball mill, and setting the rotating speed to 400rpm. After the set ball milling time is reached, separating the product from a ball milling medium in a glove box filled with argon, and storing the product in the glove box to obtain the ball milling zero-valent iron sulfide. 0.26g of ball-milled zero-valent iron sulfide was placed in a 52mL serum bottle. 26mL of morpholinoethanesulfonic acid (MES) solution at an initial pH of 6, 50mM was added to the serum bottle under anaerobic conditions. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times with oxygen-free water, 26mL of a cobalt chloride solution with the concentration of 10mM (the amount of cobalt ions is 60% of that of sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer to be subjected to rotary mixing reaction for 1h, so that cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 7
0.007g elemental sulfur powder and 0.253g zero valent iron were placed in a 52mL serum bottle (sulfur powder to zero valent iron mass ratio of 0.05). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times with oxygen-free water, 26mL of a cobalt chloride solution (the amount of cobalt ions is 60% of that of sulfur element) with a concentration of 5mM is added into a serum bottle, and the mixture is placed in a rotary mixer to be subjected to rotary mixing reaction for 1h, so that cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 8
0.058g elemental sulphur powder and 0.202g zero valent iron were placed in a 52mL serum bottle (the ratio of sulphur powder to zero valent iron mass is 0.5). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. And after the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times with oxygen-free water, 26mL of a cobalt chloride solution (the amount of cobalt ions is 60% of that of sulfur element) with a concentration of 40mM is added into a serum bottle, and the mixture is placed in a rotary mixer to be subjected to rotary mixing reaction for 1h, so that cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Example 9
0.082g elemental sulfur powder and 0.178g zero-valent iron were placed in a 52mL serum bottle (the ratio of sulfur powder to zero-valent iron mass is 0.8). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. Sealing the serum bottle, placing into a rotary mixer, and rotatingAnd mixing and reacting for 24 hours to obtain the zero-valent iron sulfide. After washing the zero-valent iron sulfide three times by using oxygen-free water, 26mL of a cobalt chloride solution with the concentration of 60mM (the content of cobalt ions is 60% of that of sulfur element) is added into a serum bottle, and the mixture is placed in a rotary mixer for rotary mixing reaction for 1h, so that the cobalt-modified zero-valent iron sulfide is obtained. Finally, the cobalt-modified zero-valent iron sulfide material is obtained through magnetic separation and natural airing.
Comparative example 1
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of morpholinoethanesulfonic acid (MES) solution at an initial pH of 6, 50mM was added to the serum bottle under anaerobic conditions. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Comparative example 2
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Comparative example 3
0.014g of elemental sulfur powder and 0.246g of zero-valent iron were placed in a 52mL serum bottle (the ratio of the amount of sulfur powder to the amount of zero-valent iron substance was 0.1). 26mL of HCl solution with an initial pH of 4 and 0.1mM were added to the serum bottle under anaerobic conditions. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 48 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Comparative example 4
Taking 0.125g of elemental sulfur powder and 2.365g of zero-valent iron in a 100mL stainless steel ball milling tank (the ratio of the sulfur powder to the zero-valent iron is 0.1), adding 50 zirconia ball milling beads (the particle size is 6 mm), filling argon into the ball milling tank as shielding gas, sealing, placing the ball milling tank on a planet ball mill, starting the ball mill, and setting the rotating speed to 400rpm. After the set ball milling time is reached, separating the product from a ball milling medium in a glove box filled with argon, and storing the product in the glove box to obtain the ball milling zero-valent iron sulfide.
Comparative example 5
0.007g elemental sulfur powder and 0.253g zero valent iron were placed in a 52mL serum bottle (sulfur powder to zero valent iron mass ratio of 0.05). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Comparative example 6
0.058g elemental sulphur powder and 0.202g zero valent iron were placed in a 52mL serum bottle. 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Comparative example 7
0.082g elemental sulfur powder and 0.178g zero-valent iron were placed in a 52mL serum bottle (the ratio of sulfur powder to zero-valent iron mass is 0.8). 26mL of MgCl with an initial pH of 6.5 and 10mM were added to the serum bottle under anaerobic conditions 2 A solution. After the serum bottle is sealed, placing the serum bottle in a rotary mixer for rotary mixing reaction for 24 hours to obtain zero-valent iron sulfide; finally, the dried vulcanized zero-valent iron material is obtained through magnetic separation and natural airing.
Application example 1
0.26g of the materials prepared in examples 1 to 9 and comparative examples 1 to 7 was taken in a 52mL serum bottle, and 26mL of ultrapure water was added in a glove box; after the serum bottle was sealed, 10ppm Trichloroethylene (TCE) was injected and then placed on a rotary mixer for reaction; the reaction conditions are 60r/min and 25 ℃; the residual amount of contaminants in the system was determined by gas chromatography (GC-FID). Two replicates were set up.
As a result, as shown in fig. 3-7, the material of the examples degraded TCE at a significantly higher rate than the material of comparative example 1. The materials of examples 1-3 can remove 100% of the TCE in 0.2h, 0.3h and 4h, respectively, while the material of comparative example 1 can remove only 80% of the TCE in 4 h. The material of example 4 can remove 95% of the TCE in 2 hours, while the material of comparative example 2 can remove only 60% of the TCE in 2 hours. The material of example 5 can remove 100% of the TCE in 0.5h, while the material of comparative example 3 can remove only 50% of the TCE in 4 h. The material of example 6 can remove 100% of the TCE in 4 hours, while the material of comparative example 4 can remove only 40% of the TCE in 10 hours. The material of example 7 can remove 100% of the TCE in 0.5h, while the material of comparative example 5 can remove only 30% of the TCE in 4 h. The material of example 8 can remove 100% of the TCE in 0.1h, while the material of comparative example 6 requires 4h to remove 100% of the TCE. The material of example 9 can remove 100% of the TCE in 0.1h, while the material of comparative example 7 requires 4h to remove 100% of the TCE. In addition, the materials of example 1 all had ethylene as the product of TCE degradation, whereas the materials of comparative example 1 had acetylene and cis-1, 2-dichloroethylene as the major products of TCE degradation. The results show that the reduction activity of the cobalt-modified zero-valent iron sulfide is obviously improved.
Application example 2
0.26g of the materials prepared in example 1 and comparative example 1 was taken in a 52mL serum bottle, and 26mL of ultrapure water was added in a glove box; after the serum bottle is sealed, 10ppm cis-1, 2-dichloroethylene (cis-DCE) is injected, and then the mixture is placed on a rotary mixer for reaction; the reaction conditions are 60r/min and 25 ℃; the residual amount of contaminants in the system was determined by gas chromatography (GC-FID). Two replicates were set up.
It was found that the material of example 1 could remove 100% of cis-DCE in 1h and that the contaminants could be all converted to ethylene. Whereas the material of comparative example 1 only removed 5% of cis-DCE in 48 hours. This indicates that the reduction activity of cobalt-modified zero-valent iron sulfide is significantly improved.
Application example 3
0.26g of the materials prepared in example 1 and comparative example 1 was taken in a 52mL serum bottle, and 26mL of ultrapure water was added in a glove box; after the serum bottle was sealed, 10ppm of 1, 2-dichloroethane (1, 2-DCA) was injected and then placed on a rotary mixer for reaction; the reaction conditions are 60r/min and 25 ℃; the residual amount of contaminants in the system was determined by gas chromatography (GC-FID). Two replicates were set up.
It was found that the material of example 1 removed 25% of 1,2-DCA in 4 d. While material 4d of comparative example 1 still failed to degrade 1,2-DCA. This indicates that the reduction activity of cobalt-modified zero-valent iron sulfide is significantly improved.
Application example 4
0.2g of the material obtained in example 1 and comparative example 1 was put into a 250mL three-necked flask, and an aqueous solution having a Cr (VI) concentration of 10ppm and 200mL was added thereto, whereby the concentration of zero valent iron sulfide in the solution was 1g/L. The experiment was performed in an open aerobic environment with mechanical stirring and mixing at a rotational speed of 500r/min. The concentration of Cr (VI) in the solution was measured by sampling at regular intervals. Cr (VI) was measured spectrophotometrically.
It was found that the material of example 1 removed 100% of Cr (VI) in 10min, whereas the material of comparative example 1 required 20h of material to completely remove Cr (VI).
Application example 5
0.1g of the material obtained in example 1 was put into a 250mL three-necked flask, and an aqueous solution of gold orange II having a concentration of 40ppm and 200mL was added thereto, whereby the concentration of zero valent iron sulfide in the solution was 0.5g/L.
The reaction is carried out in an open aerobic environment. Mechanical stirring and mixing are adopted, and the rotating speed is set to be 500r/min. Samples were taken at regular intervals to determine the concentration of azo dye in the solution. The concentration of azo dye was determined spectrophotometrically.
The research shows that the gold orange II can be completely removed within 0.5h, and the removal rate is 100%, which shows that the prepared material has good removal effect on the azo dye.
Application example 6
0.26g of the material prepared in example 1 was taken in a 52mL serum bottle, and 26mL of a 1, 4-dinitrobenzene solution in which the concentration of 1, 4-dinitrobenzene was 40ppm was added in a glove box. After the serum bottle was sealed, it was then placed on a rotary mixer for reaction at 60r/min and 25 ℃. The residual amount of 1, 4-dinitrobenzene in the system was measured by liquid chromatography. The research shows that the 1, 4-dinitrobenzene can be completely removed within 1h, and the removal rate is 100%.
Claims (6)
1. A method for preparing cobalt-modified zero-valent iron sulfide, which is characterized by comprising the following steps: under the normal temperature condition, adding the zero-valent iron sulfide into a soluble cobalt salt aqueous solution for reaction, and separating to obtain a cobalt-modified zero-valent iron sulfide material;
the preparation method of the vulcanized zero-valent iron comprises the following steps: under the normal temperature condition, adding elemental sulfur powder and zero-valent iron into an aqueous solution according to the mass ratio of 0.01-0.8:1 for mixing reaction to prepare vulcanized zero-valent iron; the aqueous solution is an acidic aqueous solution, an inorganic salt solution or a pH buffer solution;
or ball milling the elemental sulfur powder and the zero-valent iron according to the mass ratio of 0.05-0.2:1 under the normal temperature condition to obtain the vulcanized zero-valent iron.
2. The method for preparing cobalt-modified zero-valent iron sulfide according to claim 1, wherein the molar ratio of sulfur element to iron element in the zero-valent iron sulfide is 0.01-0.8:1; the addition amount of cobalt ions in the cobalt salt aqueous solution is 1-100 percent based on the molar consumption of sulfur element.
3. The method for preparing cobalt-modified zero-valent iron sulfide of claim 1, wherein the soluble cobalt salt is CoCl 2 。
4. The method of producing cobalt-modified zero-valent iron sulfide of claim 1, wherein the adding of zero-valent iron sulfide to the aqueous solution of soluble cobalt salt is performed for a period of time > 30min.
5. A cobalt-modified zero-valent iron sulfide produced by the production method according to any one of claims 1 to 4.
6. Use of cobalt-modified zero-valent iron sulfide according to claim 5 for the treatment of bodies of water contaminated with halogenated organic species, heavy metals, pesticides, azo dyes and/or nitroorganic species.
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