CN114618425B - Molybdenum disulfide/diatomite composite material and preparation method and application thereof - Google Patents
Molybdenum disulfide/diatomite composite material and preparation method and application thereof Download PDFInfo
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- diatomite
- molybdenum disulfide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000005909 Kieselgur Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- -1 mercury ions Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a molybdenum disulfide/diatomite composite material and a preparation method and application thereof. And uniformly mixing the alkali metal inorganic salt, the diatomite, the molybdenum source and the sulfur source, and calcining and washing to obtain the molybdenum disulfide/diatomite composite material. The composite material uses two-dimensional flaky molybdenum disulfide with complete morphology and alkali metal intercalation as a heavy metal adsorption active ingredient, uses diatomite with developed pores and specific structure as a carrier, and enables the molybdenum disulfide to grow on the diatomite carrier in situ, so that the whole composite material has the characteristics of developed pores, multiple adsorption active sites, good structural stability and the like, has high adsorption efficiency on heavy metals in solution, and can be widely applied to repairing heavy metal polluted water bodies.
Description
Technical Field
The invention relates to a heavy metal adsorption material, in particular to a molybdenum disulfide/diatomite composite material, a method for synthesizing the molybdenum disulfide/diatomite composite material by a one-step high-temperature solid phase method, and application of the molybdenum disulfide/diatomite composite material as a heavy metal adsorption material in heavy metal polluted water body remediation, and belongs to the technical field of heavy metal polluted water body treatment.
Background
Molybdenum disulfide is a unique two-dimensional material, which has become one of the most popular nanomaterials due to its unique optical and electronic properties. The unique two-dimensional lamellar structure enables the molybdenum disulfide to have quite high specific surface area, and a large amount of sulfur atoms are exposed on the surface of the molybdenum disulfide, and the molybdenum disulfide becomes a promising heavy metal adsorbent due to good affinity between the sulfur atoms and heavy metals, particularly cationic heavy metals. Some studies have been focused on applying molybdenum disulfide to adsorption of heavy metal ions in aqueous solutions, such as those prepared by Wang et al, 2H-type nano molybdenum disulfide, for Cd 2+ Shows good adsorption effect ("remote of Cd (II) from water by using nano-scale molybdenum disulphide sheets as adsorbents", qingmiao Wang et al Journal of Molecular Liquids,2018, 263:526-533.). Song et al Fe 3 O 4 Nanoparticle modified defective molybdenum disulfide nanosheets, and application of the nanoshelds in adsorbing Hg in aqueous solution 2+ Exhibits high adsorption capacity and excellent selectivity, etc. (Decoration of defective MoS) 2 nanosheets with Fe 3 O 4 nanoparticles as superior magnetic adsorbent for highly selective and efficient mercury ions(Hg 2+ ) remote ", YIheng Song et al Journal of Alloys and Compounds,2018,737:113-121. Wang et al synthesized a polyvinylpyrrolidone intercalated molybdenum disulfide composite and a polyacrylamide intercalated molybdenum disulfide composite, and the results showed that at ph=5, the adsorption amounts of both composites to Cr (VI) were 142.24mg/g and 84.91mg/g, respectively ("Polyvinylpyrrolidone and polyacrylamide intercalated molybdenum disulfide as adsorbents for enhanced removal of chromium (VI) from aqueous solutions", jian Wang et al, chemical Engineering Journal,2018, 334:569-578.) these studies focused mainly on improving adsorption performance by optimizing adsorption conditions or preparing molybdenum disulfide-based composites. However, these modification means for molybdenum disulfide are complicated to operate and difficult to apply on a large scale. The diatomite has unique ordered microporous structure, high porosity and adsorptionThe carrier material used as the adsorbent is widely applied to the removal of heavy metals in aqueous solution. In order to obtain diatomite with higher porosity and improve the adsorption capacity, researchers adopt some modification methods, such as Zhang Xinyu et al, for example, microwave, ultrasonic and acidification to prepare the micro super acid modified diatomite, and under the same conditions, the modified diatomite has the adsorption capacity to Pb 2+ 、Cu 2+ 、Cd 2+ The adsorption performance of the modified diatomite is stronger than that of natural diatomite (the modified diatomite modified by 'micro super acid' has Pb 2+ ,Cu 2+ ,Cd 2+ Adsorption Performance research of (A), zhang Xinyu et al, university of southwest (Nature science edition), 2018,43 (09): 90-94.). Wang Jiao et al use acid leaching and roasting to purify diatomaceous earth, the specific surface area after purification is remarkably increased, and the adsorption performance to formaldehyde is remarkably improved ("research on the influence of acid leaching and roasting on the adsorption performance of diatomaceous earth on formaldehyde", wang Jiao et al, nonmetallic ore 2011,34 (06): 72-74.). Zheng Cuixia et al treat aniline wastewater with hydrochloric acid modified diatomite, so that the concentration of aniline in 50mL of wastewater can be reduced from 50mg/L to 4.6mg/L, and the removal rate can reach 90.5% at maximum (research on treating aniline-containing wastewater by modified diatomite, zheng Cuixia, etc., jiangxi chemical industry, 2020,36 (05): 63-65.). Liu Fengyu et al use sodium hydroxide modified diatomite to treat zinc-containing wastewater, and the removal rate of the modified diatomite for zinc under the optimal condition can reach 96.0% ("research on modified diatomite to treat zinc-containing wastewater" Liu Fengyu, liaoning chemical industry, 2018,47 (03): 186-188.). These conventional modification methods are single-acting and require stepwise progress and complicated operations.
Most of the above methods reported in the prior art require complicated operation steps and severe process conditions, thereby increasing the manufacturing cost of the molybdenum disulfide/diatomite composite material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a molybdenum disulfide/diatomite composite material, wherein the composite material uses two-dimensional flaky molybdenum disulfide with complete morphology and alkali metal intercalation as a heavy metal adsorption active ingredient, uses diatomite with developed pores and specific structure as a carrier, and the molybdenum disulfide grows on the diatomite carrier in situ, so that the molybdenum disulfide composite material has the characteristics of developed pores, more adsorption active sites, good structural stability and the like, and has high adsorption efficiency on heavy metals in solution.
The second aim of the invention is to provide a preparation method of the molybdenum disulfide/diatomite composite material, which has simple process and lower cost and is beneficial to large-scale production.
The third purpose of the invention is to provide the application of the molybdenum disulfide/diatomite composite material as the heavy metal adsorption material in the remediation of heavy metal pollutant water bodies, wherein the molybdenum disulfide/diatomite composite material has the advantages of low dosage, mild adsorption condition, high adsorption activity, capacity of achieving large-capacity adsorption in a short time, recovery and reutilization potential, and suitability for large-scale popularization and use in the specific application process.
In order to achieve the technical aim, the invention provides a preparation method of a molybdenum disulfide/diatomite composite material, which is obtained by uniformly mixing alkali metal inorganic salt, diatomite, a molybdenum source and a sulfur source, calcining and washing.
The preparation process of the molybdenum disulfide/diatomite composite material is completed through one-step high-temperature solid phase reaction, in the high-temperature solid phase reaction process, a molybdenum source and a sulfur source mainly generate molybdenum disulfide through oxidation-reduction and other reactions, diatomite is used as a carrier of the molybdenum disulfide, meanwhile, the in-situ generation of the molybdenum disulfide on the surface of the diatomite is realized, and the loading stability of the molybdenum disulfide on the surface of the diatomite is greatly improved. While alkali metal inorganic salts can form a liquid molten medium under high temperature conditions, they mainly play the following roles: on one hand, the salt melt can provide a liquid reaction environment for a molybdenum source and a sulfur source to promote the generation of molybdenum disulfide, and simultaneously, the high-temperature liquid phase environment can synchronously pretreat the diatomite carrier to improve the porosity and the surface activity of the diatomite carrier and prevent the mutual agglomeration among particles; on the other hand, as a fused salt template, a template is provided for molybdenum disulfide crystal growth, so that molybdenum disulfide grows into a special crystal morphology structure, such as two-dimensional molybdenum disulfide nano sheets which grow perpendicular to the surface of diatomite and are arranged in an unordered manner in FIG. 2; in the third aspect, in the high-temperature solid-phase reaction process, free alkali metal ions can carry out intercalation modification on molybdenum disulfide, so that the heavy metal adsorption performance of the material is improved.
The key of the technical scheme of the invention is that the alkali metal inorganic salt is utilized to form a liquid melting medium in a high-temperature environment, the diatomite carrier can be pretreated in a high-temperature process, the porosity and the surface activity of the diatomite carrier are improved, the liquid molten salt can provide a reaction environment for a molybdenum source and a sulfur source, the mutual agglomeration among particles can be prevented, and meanwhile, free alkali metal ions can enter an interlayer structure of molybdenum disulfide, so that the modification of the molybdenum disulfide is realized, and the molybdenum disulfide/diatomite composite material with high adsorption performance is obtained.
As a preferred embodiment, the alkali metal inorganic salt is at least one of lithium chloride, sodium chloride and potassium chloride. Preferred alkali metal inorganic salts are the usual alkali metal halogen salts which have melting points substantially between 600 and 800 c and which readily form a molten liquid phase under the high temperature reaction conditions of the present invention.
As a preferred embodiment, the molybdenum source is at least one of sodium molybdate and ammonium molybdate tetrahydrate.
As a preferred embodiment, the sulfur source is thiourea. The preferred molybdenum source is common molybdate, the sulfur source is thiourea, and molybdenum contained in the molybdate is high-valence molybdenum and can undergo oxidation-reduction reaction with thiourea to form molybdenum disulfide.
As a preferred embodiment, the molar ratio of the molybdenum source to the sulfur source is 1:2 to 1:8.
As a preferable scheme, the mass ratio of the molybdenum source to the diatomite is 1:1-1:10;
as a preferable scheme, the mass ratio of the diatomite to the alkali metal inorganic salt is 1:20-1:50. The proportion of the alkali metal inorganic salt is greatly excessive relative to the proportion of the diatomite, and the molten liquid phase generated at high temperature of the alkali metal inorganic salt is mainly used as a medium, so that the purposes of promoting the generation of molybdenum disulfide, improving the loading effect of the diatomite on the molybdenum disulfide, improving the crystal structure of the molybdenum disulfide and realizing the intercalation modification of the molybdenum disulfide are achieved.
As a preferable scheme, the diatomite is in a disc-shaped structure, and the diameter of the disc is smaller than 40 mu m. The diameter of the wafer is preferably 20 to 30. Mu.m.
As a preferred embodiment, the calcination conditions are as follows: the reaction temperature is 700-900 ℃ and the reaction time is 0.5-5 h. Calcination can be directly reacted in an air atmosphere, and when the reaction temperature is too low, it is difficult to make the alkali metal inorganic salt form a molten state, and when the temperature is too high, volatilization of the salt and heat loss are caused.
As a preferred embodiment, the washing is performed by deionized water and ethanol, mainly for removing alkali metal inorganic salts.
The invention also provides a molybdenum disulfide/diatomite composite material, which is obtained by the preparation method.
The molybdenum disulfide/diatomite composite material provided by the invention is composed of a diatomite carrier and a molybdenum disulfide material grown on the diatomite carrier in situ. The surface of the diatomite carrier is distributed with a uniform and through hole structure, the diatomite carrier is of a disc structure, and the diameter of the diatomite carrier is 20-30 mu m. Molybdenum disulfide is a two-dimensional nano sheet structure, grows irregularly perpendicular to the surface of diatomite, builds a large number of pore structures, and can expose more adsorption active sites. And the activity of adsorbing heavy metals is obviously improved after the molybdenum disulfide is subjected to intercalation modification of alkali metal salt.
The invention also provides application of the molybdenum disulfide/diatomite composite material as a heavy metal adsorption material in water heavy metal pollution remediation.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the molybdenum disulfide/diatomite composite material provided by the invention is characterized in that a flaky molybdenum disulfide material is formed in situ on the holes and the surface of diatomite, and the composite material can effectively improve the adsorption performance of heavy metals in an aqueous solution of the material based on the cooperation between components and special structures among the components. The diatomite in the composite material has a developed pore structure, can provide attachment points for molybdenum disulfide well after high-temperature treatment, and has good adsorption performance on heavy metal, the two-dimensional flaky molybdenum disulfide material is prepared by a molten salt template method, has complete morphology and more heavy metal adsorption sites, and the alkali metal intercalated molybdenum disulfide material has stronger adsorption capacity on the heavy metal. In conclusion, the molybdenum disulfide/diatomite composite material has developed pores, the molybdenum disulfide subjected to alkali metal intercalation has a good adsorption effect on heavy metal pollution, has long-term effectiveness and stability on the restoration effect of heavy metal pollutants in aqueous solution, and provides a basis and reference for restoration of heavy metal polluted water.
2. The method for preparing the molybdenum disulfide/diatomite composite material is completed through one-step high-temperature calcination, has simple process, no harmful waste, abundant raw materials and low production cost, and is beneficial to large-scale production.
3. The application of the molybdenum disulfide/diatomite composite material provided by the invention has the advantages that the molybdenum disulfide/diatomite composite material is used as a heavy metal adsorption material for repairing heavy metal pollution of a water body, the dosage of the composite material is low, the adsorption condition is mild, the adsorption activity is high, the high-capacity adsorption can be achieved in a short time, the recycling potential is realized, and the large-scale popularization and the use are facilitated.
Drawings
FIG. 1 is an X-ray diffraction pattern of the molybdenum disulfide/diatomaceous earth composite in example 1.
Fig. 2 is a scanning electron microscope image of the molybdenum disulfide/diatomaceous earth composite in example 1.
Fig. 3 is an X-ray diffraction pattern of the composite material in example 8.
FIG. 4 is a graph of Pb in a molybdenum disulfide/diatomaceous earth composite of example 9 2+ The drawing is sucked.
Detailed Description
In order to better explain the technical scheme and advantages of the present invention, the present invention will be further described in detail with reference to the following examples. It is noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as will be apparent to those skilled in the art upon examination of the foregoing disclosure.
Example 1
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of kieselguhr and 40g of lithium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, heat preservation is carried out for 2h at 750 ℃, and natural cooling is carried out, thus obtaining a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 70min and the maximum absorption amount is 96.3mg/L, and the pH=6.
Example 2
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of kieselguhr and 40g of sodium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 850 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 68min, and the maximum absorption amount is 99.5mg/L.
Example 3
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of kieselguhr and 40g of potassium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 850 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the pH=6, the adsorption amount is stable after 75min, and the maximum adsorption amount is 105.2mg/L, and the adsorption amount is shown in figure 3.
Example 4
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite, 20g of lithium chloride and 20g of sodium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 750 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 77min and the maximum absorption amount is 106.5mg/L, and the pH=6.
Example 5
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite, 20g of lithium chloride and 20g of potassium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 750 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 78min and the maximum absorption amount is 115.6mg/L.
Example 6
2.4g of sodium molybdate dihydrate, 3.8g of thiourea and 12.0g of diatomite are added into a corundum crucible, and after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 750 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 75min, and the maximum absorption amount is 108.4mg/L.
Example 7
2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite, 15g of lithium chloride, 15g of sodium chloride and 15g of potassium chloride are added into a corundum crucible, after being uniformly mixed, the mixture is placed into a muffle furnace, and the mixture is kept at 750 ℃ for 2 hours and naturally cooled, so that a sintered product is obtained. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the pH=6, the adsorption amount is stable after 80min, and the maximum adsorption amount is 134.8mg/L, and the adsorption amount is shown in FIG. 3.
Example 8 (comparative example)
2.4g of sodium molybdate dihydrate, 3.8g of thiourea and 12.0g of diatomite are added into a corundum crucible, and after being uniformly mixed, the mixture is placed into a muffle furnace, and the temperature is kept for 2 hours at 750 ℃, and the mixture is naturally cooled to obtain a sintered product. And (3) cleaning the product with deionized water and absolute ethyl alcohol for 5 times respectively, drying at 60 ℃ for 12 hours, grinding and collecting to obtain the composite material. As can be seen from FIG. 3, no molybdenum disulfide phase appears in the composite material, namely, no molybdenum disulfide is generated, and the molybdenum disulfide/diatomite composite materials are obviously different from the molybdenum disulfide/diatomite composite materials prepared in examples 1-7.
Application of the prepared composite material to Pb in aqueous solution 2+ Is 1.5g/L, pb 2+ The concentration of the solution is 200mg/L, the temperature is 25 ℃, the absorption amount is stable after 75min, and the maximum absorption amount is 34.7mg/L.
Claims (4)
1. The application of the molybdenum disulfide/diatomite composite material is characterized in that: the molybdenum disulfide/diatomite composite material is used as a heavy metal adsorption material and applied to restoration of heavy metal pollution of water body;
the molybdenum disulfide/diatomite composite material is prepared by the following preparation method: mixing alkali metal inorganic salt, diatomite, molybdenum source and sulfur source uniformly, calcining, and washing to obtain the catalyst; the conditions of the calcination are as follows: the reaction temperature is 700-900 ℃ and the reaction time is 0.5-5 h; the alkali metal inorganic salt is at least one of lithium chloride, sodium chloride and potassium chloride.
2. The use of a molybdenum disulfide/diatomaceous earth composite according to claim 1, wherein: the molybdenum source is at least one of sodium molybdate and ammonium molybdate tetrahydrate.
3. The use of a molybdenum disulfide/diatomaceous earth composite according to claim 1, wherein: the sulfur source is thiourea.
4. The application of the molybdenum disulfide/diatomite composite material according to any one of claims 1-3, wherein the application is characterized in that:
the molar ratio of the molybdenum source to the sulfur source is 1:2-1:8;
the mass ratio of the molybdenum source to the diatomite is 1:1-1:10;
the mass ratio of the diatomite to the alkali metal inorganic salt is 1:20-1:50.
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