CN114618425A - 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 94
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
- 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 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 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
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000005067 remediation Methods 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 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
- 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
- 239000003054 catalyst Substances 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
- 239000011148 porous material Substances 0.000 abstract description 8
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000002687 intercalation Effects 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001816 cooling 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
- 230000008569 process Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- -1 mercury ions Chemical class 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002351 wastewater 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
- 239000002135 nanosheet Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000004064 recycling Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 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
- 229920002401 polyacrylamide Polymers 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
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J20/0274—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
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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
- B01J20/10—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention discloses a molybdenum disulfide/diatomite composite material and a preparation method and application thereof. And uniformly mixing alkali metal inorganic salt, diatomite, a molybdenum source and a sulfur source, calcining and washing to obtain the molybdenum disulfide/diatomite composite material. The composite material takes two-dimensional flaky molybdenum disulfide with complete appearance and alkali metal intercalation as a heavy metal adsorption active ingredient, takes diatomite with developed pores and a specific structure as a carrier, and the molybdenum disulfide grows on the diatomite carrier in situ, so that the composite material has the characteristics of developed pores, more adsorption active sites, good structural stability and the like, shows high adsorption efficiency on heavy metals in a solution, and can be widely applied to heavy metal polluted water body remediation.
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 the 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, and has become one of the most popular nanomaterials due to unique optical and electronic properties of the molybdenum disulfide. The unique two-dimensional sheet structure enables the molybdenum disulfide to have quite high specific surface area, a large number of sulfur atoms are exposed on the surface of the molybdenum disulfide, and the molybdenum disulfide becomes a promising heavy metal adsorbent due to the good affinity between the sulfur atoms and heavy metals, particularly cationic heavy metals. Some researches have been devoted to applying molybdenum disulfide to the adsorption of heavy metal ions in aqueous solution, such as Wang et al prepared 2H type nano molybdenum disulfide, to Cd2+Shows good adsorption effect ("Removal of Cd (II) from water by using nano-scale catalyst sheets as adsorbents", Qingmiao Wang et al, Journal of Molecular Liquids,2018,263: 526-. Fe for Song et al3O4Nanoparticle modified defective molybdenum disulfide nanosheet, and application of nano hybrid in adsorption of Hg in aqueous solution2+Exhibit high adsorption capacity and excellent selectivity (desorption of defective MoS)2nanosheets with Fe3O4 nanoparticles as superior magnetic adsorbent for highly selective and efficient mercury ions(Hg2+) removal ", Yiheng Song et al, Journal of Alloys and Compounds,2018,737: 113-. Wang et al synthesized a polyvinylpyrrolidone-intercalated molybdenum disulfide composite and a polyacrylamide-intercalated molybdenum disulfide composite, and showed that at pH 5, the two composites adsorbed Cr (VI) in amounts of 142.24mg/g and 84.91mg/g, respectively ("Pol)The studies of yvinylpyrrodidone and polyacrylamide interlocked molybdenum disulfide as additives for enhanced removal of chlorine (VI) from aqueous solvents ", Jian Wang et al, Chemical Engineering Journal,2018,334: 569-. However, the modification means aiming at the molybdenum disulfide has complex operation mode and is difficult to be applied on a large scale. The diatomite has the advantages of unique orderly arranged microporous structure, high porosity, strong adsorption performance, low cost and the like, so the diatomite is widely used as a carrier material of the adsorbent to remove heavy metals in aqueous solution. In order to obtain diatomite with higher porosity to improve the adsorption capacity, researchers will adopt some modification methods, such as Zhang et al, to prepare 'micro super acid' modified diatomite through microwave, ultrasonic and acidification, and the modified diatomite reacts with Pb under the same conditions2+、Cu2+、Cd2+The adsorption performance of the diatomite is stronger than that of natural diatomite ('micro super acid' modified diatomite to Pb2+,Cu2+,Cd2+The study on the adsorption performance of the adsorbent of (1)', Zhang Xin et al, school news of southwest university (Nature science edition), 2018,43(09): 90-94.). Wangzou et al have adopted acid leaching and roasting methods to purify diatomite, and have remarkably increased specific surface area and obviously improved formaldehyde adsorption performance after purification ("research on influence of acid leaching and roasting on formaldehyde adsorption performance of diatomite", Wangzou et al, nonmetallic minerals, 2011,34(06): 72-74.). Zhengcuixia et al can reduce the aniline concentration in 50mL waste water from 50mg/L to 4.6mg/L by using hydrochloric acid modified diatomite, and the removal rate can reach 90.5% at most (research on treating aniline-containing waste water by modified diatomite, Zhengcuixia et al, Jiangxi chemical industry, 2020,36(05): 63-65.). Liufeng feather and the like adopt sodium hydroxide modified diatomite to treat zinc-containing wastewater, and the removal rate of the modified diatomite to zinc can reach 96.0% under the optimal condition (research on treating the zinc-containing wastewater by the modified diatomite, Liufeng feather and the like, Liaoning chemical engineering, 2018,47(03): 186-188.). These conventional modification methods are single-acting and require stepwise operation, which is complicated.
Most of the methods reported in the prior art need more complicated operation steps and harsh process conditions, so that the manufacturing cost of the molybdenum disulfide/diatomite composite material is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a molybdenum disulfide/diatomite composite material, wherein the composite material takes two-dimensional flaky molybdenum disulfide with complete appearance and alkali metal intercalation as a heavy metal adsorption active ingredient, takes diatomite with developed pores and a specific structure as a carrier, and the molybdenum disulfide grows on the diatomite carrier in situ, so that the dispersibility is good, the combination is stable, the whole composite material has the characteristics of developed pores, more adsorption active sites, good structural stability and the like, and the composite material has high adsorption efficiency on heavy metals in a solution.
The second purpose of the invention is to provide a preparation method of the molybdenum disulfide/diatomite composite material, which has the advantages of simple process and lower cost and is beneficial to large-scale production.
The third purpose of the invention is to provide an application of the molybdenum disulfide/diatomite composite material as a heavy metal adsorption material in heavy metal pollutant water body remediation, and the molybdenum disulfide/diatomite composite material has the advantages of low consumption, mild adsorption conditions, high adsorption activity, capacity of achieving large-capacity adsorption in a short time, potential of recycling and reutilization, and contribution to large-scale popularization and use in the specific application process.
In order to realize the technical purpose, the invention provides a preparation method of a molybdenum disulfide/diatomite composite material, which comprises the steps of uniformly mixing alkali metal inorganic salt, diatomite, a molybdenum source and a sulfur source, calcining and washing to obtain the molybdenum disulfide/diatomite composite material.
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 are mainly used for generating molybdenum disulfide through reactions such as oxidation reduction and the like, diatomite is used as a carrier of the molybdenum disulfide, the in-situ generation of the molybdenum disulfide on the surface of the diatomite is realized, and the load stability of the molybdenum disulfide on the surface of the diatomite is greatly improved. The alkali metal inorganic salt can form a liquid molten medium under the high-temperature condition, and the alkali metal inorganic salt mainly plays the following roles: on one hand, the salt melt can provide a liquid reaction environment for the molybdenum source and the sulfur source to promote the generation of molybdenum disulfide, and meanwhile, 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 mutual agglomeration of particles; on the other hand, as a molten salt template, a template is provided for the growth of molybdenum disulfide crystals, so that molybdenum disulfide grows into a special crystal morphology structure, such as two-dimensional molybdenum disulfide nanosheets growing perpendicularly to the surface of diatomite and arranged in a disordered manner in fig. 2; in the third aspect, in the high-temperature solid-phase reaction process, free alkali metal ions can perform intercalation modification on molybdenum disulfide, so that the heavy metal adsorption performance of the material is improved.
The key point of the technical scheme is that alkali metal inorganic salt is utilized to form a liquid molten medium in a high-temperature environment, the diatomite carrier can be pretreated in the 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, mutual agglomeration among particles can be prevented, free alkali metal ions can enter an interlayer structure of molybdenum disulfide, the modification of the molybdenum disulfide is realized, and the molybdenum disulfide/diatomite composite material with high adsorption performance is obtained.
As a preferable embodiment, the alkali metal inorganic salt is at least one of lithium chloride, sodium chloride and potassium chloride. The preferred alkali metal inorganic salts are the common alkali metal halide salts which have melting points substantially between 600 and 800 ℃ and are susceptible to forming a molten liquid phase under the high temperature reaction conditions of the present invention.
In 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 a common molybdate, the sulfur source is thiourea, and the molybdenum contained in the molybdate is high-valence molybdenum which can perform oxidation-reduction reaction with thiourea to form molybdenum disulfide.
Preferably, 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;
preferably, 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 a molten liquid phase generated at high temperature of the alkali metal inorganic salt is mainly used as a medium, so that the aims 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 fulfilled.
Preferably, the diatomite is of a disc-shaped structure, and the diameter of the disc is less than 40 μm. The diameter of the wafer is preferably 20 to 30 μm.
As a preferred embodiment, the calcination conditions are: the reaction temperature is 700-900 ℃, and the reaction time is 0.5-5 h. The calcination can be directly reacted in an air atmosphere, and if the reaction temperature is too low, it is difficult to form the alkali metal inorganic salt into a molten state, and if the temperature is too high, volatilization of the salt and heat loss are caused.
As a preferred scheme, the washing is washing by deionized water and ethanol, and mainly removing alkali metal inorganic salt.
The invention also provides a molybdenum disulfide/diatomite composite material, which is obtained by the preparation method.
The molybdenum disulfide/diatomite composite material is composed of a diatomite carrier and a molybdenum disulfide material growing on the diatomite carrier in situ. The surface of the diatomite carrier is distributed with uniform and through hole structures, and the diatomite carrier is of a wafer structure and has the diameter of 20-30 mu m. The molybdenum disulfide is of a two-dimensional nano flaky structure and grows out of order perpendicular to the surface of the diatomite, a large number of pore structures are constructed, and more adsorption active sites can be exposed. And after the molybdenum disulfide is subjected to intercalation modification of alkali metal salt, the activity of adsorbing heavy metal is obviously improved.
The invention also provides application of the molybdenum disulfide/diatomite composite material as a heavy metal adsorption material to restoration of heavy metal pollution of a water body.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the molybdenum disulfide/diatomite composite material provided by the invention is a flaky molybdenum disulfide material formed in situ in the pores and the surface of diatomite, and the composite material can effectively improve the heavy metal adsorption performance in the aqueous solution of the material based on the components and the synergy between special structures of the components. The diatomite in the composite material has a developed pore structure, can well provide attachment points for molybdenum disulfide after high-temperature treatment, and has good adsorption performance on heavy metals, the two-dimensional flaky molybdenum disulfide material is prepared by a molten salt template method, the appearance is complete, the heavy metal adsorption sites are more, and the molybdenum disulfide material with the alkali metal intercalation has stronger adsorption capacity on the heavy metals. In conclusion, the molybdenum disulfide/diatomite composite material has developed pores, the molybdenum disulfide after the alkali metal intercalation has a good adsorption effect on heavy metal pollution, and the molybdenum disulfide/diatomite composite material has long-term effectiveness and stability on the repair effect of heavy metal pollutants in an aqueous solution, thereby providing a basis and reference for realizing the repair of a heavy metal polluted water body.
2. The method for preparing the molybdenum disulfide/diatomite composite material is completed by one-step high-temperature calcination, has the advantages of simple process, no harmful waste, rich raw materials and low production cost, and is favorable for large-scale production.
3. The application of the molybdenum disulfide/diatomite composite material provided by the invention applies the molybdenum disulfide/diatomite composite material as a heavy metal adsorption material to the remediation of heavy metal pollution in water, the composite material is low in consumption, mild in adsorption condition and high in adsorption activity, can achieve large-capacity adsorption in a short time, has the potential of recycling, and is beneficial to large-scale popularization and use.
Drawings
FIG. 1 is an X-ray diffraction pattern of the molybdenum disulfide/diatomaceous earth composite material of example 1.
FIG. 2 is a scanning electron microscope image of the molybdenum disulfide/diatomite composite material of example 1.
FIG. 3 is an X-ray diffraction pattern of the composite material of example 8.
FIG. 4 is the Pb pair of the molybdenum disulfide/diatomite composite material of example 92+And (5) absorbing the attached drawings.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
Example 1
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite and 40g of lithium chloride into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the heat at 750 ℃ for 2 hours, and naturally cooling to obtain a fired product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration is 200mg/L, the temperature is 25 ℃, the pH value is 6, the adsorption capacity tends to be stable after 70min, and the maximum adsorption capacity is 96.3 mg/L.
Example 2
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite and 40g of sodium chloride into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the heat at 850 ℃ for 2 hours, and naturally cooling to obtain a fired product. And (3) washing the product with deionized water and absolute ethyl alcohol for 5 times respectively, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Adsorption of (2), the solid-to-liquid ratio is 1.5g/L, Pb2+The solution concentration is 200mg/L and the temperature isThe adsorption capacity tends to be stable after 68min at 25 ℃ and pH 6, and the maximum adsorption capacity is 99.5 mg/L.
Example 3
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite and 40g of potassium chloride into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the heat at 850 ℃ for 2 hours, and naturally cooling to obtain a fired product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration was 200mg/L, the temperature was 25 ℃, and the pH was 6, and the adsorption capacity became stable after 75min, with the maximum adsorption capacity of 105.2mg/L, as shown in fig. 3.
Example 4
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite, 20g of lithium chloride and 20g of sodium chloride into a corundum crucible, uniformly mixing, placing in a muffle furnace, preserving the temperature for 2 hours at 750 ℃, and naturally cooling to obtain a fired product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration is 200mg/L, the temperature is 25 ℃, the pH value is 6, the adsorption capacity tends to be stable after 77min, and the maximum adsorption capacity is 106.5 mg/L.
Example 5
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea, 12.0g of diatomite, 20g of lithium chloride and 20g of potassium chloride into a corundum crucible, uniformly mixing, placing in a muffle furnace, preserving the temperature for 2 hours at 750 ℃, and naturally cooling to obtain a fired product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
Applying the prepared composite material to water solutionPb in liquid2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration is 200mg/L, the temperature is 25 ℃, the pH value is 6, the adsorption capacity tends to be stable after 78min, and the maximum adsorption capacity is 115.6 mg/L.
Example 6
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea and 12.0g of diatomite into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the heat at 750 ℃ for 2 hours, and naturally cooling to obtain a sintered product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration is 200mg/L, the temperature is 25 ℃, the pH value is 6, the adsorption capacity is stable after 75min, and the maximum adsorption capacity is 108.4 mg/L.
Example 7
Adding 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 into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the temperature for 2 hours at 750 ℃, and naturally cooling to obtain a fired product. And respectively cleaning the product with deionized water and absolute ethyl alcohol for 5 times, then drying for 12 hours at the temperature of 60 ℃, grinding and collecting to obtain the molybdenum disulfide/diatomite composite material.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration was 200mg/L, the temperature was 25 ℃, and the pH was 6, and the adsorption capacity became stable after 80min, with the maximum adsorption capacity being 134.8mg/L, as shown in fig. 3.
Example 8 (comparative example)
Adding 2.4g of sodium molybdate dihydrate, 3.8g of thiourea and 12.0g of diatomite into a corundum crucible, uniformly mixing, placing the mixture into a muffle furnace, preserving the heat at 750 ℃ for 2 hours, and naturally cooling to obtain a sintered product. Washing the product with deionized water and anhydrous ethanol for 5 times respectively, drying at 60 deg.C for 12 hr, grinding, and collecting to obtain the composite material. As can be seen from FIG. 3, no molybdenum disulfide phase appears in the composite material, i.e., no molybdenum disulfide is generated, which is obviously different from the molybdenum disulfide/diatomite composite materials prepared in the embodiments 1-7.
The prepared composite material is applied to Pb in aqueous solution2+Has a solid-to-liquid ratio of 1.5g/L and Pb2+The solution concentration is 200mg/L, the temperature is 25 ℃, the pH value is 6, the adsorption capacity is stable after 75min, and the maximum adsorption capacity is 34.7 mg/L.
Claims (8)
1. A preparation method of a molybdenum disulfide/diatomite composite material is characterized by comprising the following steps: and uniformly mixing alkali metal inorganic salt, diatomite, a molybdenum source and a sulfur source, calcining and washing to obtain the catalyst.
2. The method for preparing the molybdenum disulfide/diatomite composite material according to claim 1, wherein: the alkali metal inorganic salt is at least one of lithium chloride, sodium chloride and potassium chloride.
3. The method for preparing the molybdenum disulfide/diatomite composite material according to claim 1, wherein: the molybdenum source is at least one of sodium molybdate and ammonium molybdate tetrahydrate.
4. The method for preparing the molybdenum disulfide/diatomite composite material according to claim 1, wherein: the sulfur source is thiourea.
5. The method for preparing the molybdenum disulfide/diatomite composite material according to any one of claims 1 to 4, wherein:
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.
6. The method for preparing the molybdenum disulfide/diatomite composite material as claimed in claim 1, wherein the calcination conditions are as follows: the reaction temperature is 700-900 ℃, and the reaction time is 0.5-5 h.
7. A molybdenum disulfide/diatomite composite material is characterized in that: the preparation method of any one of claims 1 to 6.
8. The use of the molybdenum disulfide/diatomite composite material as set forth in claim 7, wherein: the heavy metal adsorption material is applied to the remediation of the heavy metal pollution of the water body.
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