CN114259981B - Clay mineral loaded molybdenum disulfide composite material and preparation method and application thereof - Google Patents
Clay mineral loaded molybdenum disulfide composite material and preparation method and application thereof Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 108
- 239000002734 clay mineral Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 22
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 23
- 239000000440 bentonite Substances 0.000 claims description 22
- 229910000278 bentonite Inorganic materials 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011733 molybdenum Substances 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 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 group [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 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 239000002245 particle Substances 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 44
- 239000004480 active ingredient Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004113 Sepiolite Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052624 sepiolite Inorganic materials 0.000 description 6
- 235000019355 sepiolite Nutrition 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- -1 transition metal disulfide Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- 229940019931 silver phosphate Drugs 0.000 description 2
- 229910000161 silver phosphate Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a clay mineral loaded molybdenum disulfide composite material, and a preparation method and application thereof. The clay mineral loaded molybdenum disulfide composite material is formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier, the composite material takes clay minerals with developed pores and high specific surface area as the carrier, and the heavy metal adsorption active ingredient molybdenum disulfide active nano-sheets are assembled into flower-shaped microspheres, so that the composite material has stable structural morphology, is highly dispersed on the carrier, has high exposure of active sites, shows good adsorption performance on heavy metals, and is suitable for being applied as a heavy metal pollution water body restoration material.
Description
Technical Field
The invention relates to an adsorption material, in particular to a clay mineral loaded molybdenum disulfide composite material, a preparation method thereof and application thereof in the aspect of heavy metal polluted water body restoration, belonging to the field of environmental functional materials,
Background
Molybdenum disulfide is a typical lamellar transition metal disulfide, each layer consists of two sulfur sheets and a built-in molybdenum sheet, and is similar to a sandwich structure, the layers are connected by Van der Waals force, and the molybdenum disulfide is easy to separate and has three crystal forms of 1T, 2H and 3R due to different stacking modes, so that the molybdenum sulfide has the most stable property. Common preparation methods are mechanical stripping, liquid stripping, chemical stripping, electrochemical stripping, chemical vapor deposition and hydrothermal synthesis. The former four methods are to prepare the molybdenum disulfide nanosheets by stripping the massive molybdenum disulfide by decomposing weak Van der Waals force between layers, and the latter method is to synthesize the molybdenum disulfide nanosheets by utilizing a molybdenum source and a sulfur source. Molybdenum disulfide is a typical n-type semiconductor, has a unique electronic energy band structure, and has excellent photocatalytic performance. As a two-dimensional material, molybdenum disulfide has a large interlayer spacing and excellent electrochemical performance, and is widely used for storing energy sources of lithium ion batteries. In addition, the method has wide application in the fields of field effect transistors, sensors, photodetectors, adsorption and the like.
Because of the unique two-dimensional structure, the two-dimensional molybdenum disulfide has a huge specific surface area, has become one of the most popular adsorbents since 2010, and sulfur atoms are exposed, so that the two-dimensional molybdenum disulfide has better adsorption capacity on metals. Liu and the like adopt ultrasonic liquid phase assisted stripping and hydrothermal synthesis to prepare two types of molybdenum disulfide nanosheets, the adsorption effect of different morphologies on Pb 2+ is explored, the result shows that under the condition of low concentration (60 mg/L), the removal rate of Pb 2+ is 98.4% and 20.6%, the adsorption capacity of the molybdenum disulfide prepared by the hydrothermal synthesis can reach 174.2mg/g("Role of structural characteristics of MoS2nanosheets on Pb2+removal in aqueous solution",LIU,Y,et al.,Environmental Technology&Innovation,2021,22(14–15):101385).Chen and other structural bond molybdenum disulfide/lignin composite materials for removing Cr (VI) in water environment, the composite materials have remarkable Cr (VI) removal effect at pH=2 and T=298.15 k and 20mg/L, the adsorption capacity is 198.70mg/g, Cr(Ⅵ)("Constructing MoS2/Lignin-derived Carbon Nanocomposites for Highly Efficient Removal of Cr(VI)from Aqueous Environment",CHEN,H,et al.,Journal of Hazardous Materials,2020,408(49):124847).Paul and the like of 99.35 can be removed in 30min, cd 2+ in water is removed by using cysteine, and the result shows that molybdenum disulfide prepared by the hydrothermal method can be loaded on carbon aerogel by Guo Qinming of Cd2+("Few-layer molybdenum disulfide nanosheets functionalized with L-cysteine for selective capture of Cd2+ions",BAZYLEWSKI,P,et al.,Flatchem,2018,11:15-23). university of 76+/-15 mg/g, and used for removing Cr (VI) in water, the removal capacity is up to 460.2mg/g, and the molybdenum disulfide has excellent reusability ("S 2/S and the preparation performance of Mo02-212, and the like). Zhong Weihong and the like are used for preparing molybdenum disulfide by a molten salt method, then the molybdenum disulfide is compounded with silver phosphate, and the prepared material can absorb 628.93mg/g of iodine ions (the adsorption performance test research of silver phosphate/molybdenum disulfide on iodine ions, bells and the like, hydrometallurgy, 2019,38 (06): 476-484). Although molybdenum disulfide is more applied to the removal of metal ions, the shape of the molybdenum disulfide which is generally prepared is not easy to regulate and control, the dispersibility is poor, and the molybdenum disulfide is limited by cost and has no wide application compared with the traditional adsorbents such as activated carbon.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a composite material formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier, wherein the composite material takes clay minerals with developed pores and high specific surface area as the carrier, and heavy metal adsorption active ingredient molybdenum disulfide nano-sheets are assembled into flower-shaped microspheres, the structure is stable in appearance, the molybdenum disulfide nano-sheets are highly dispersed on the carrier, active sites are highly exposed, and good adsorption performance on heavy metals is shown.
The second aim of the invention is to provide a method for preparing the clay mineral loaded molybdenum disulfide composite material, which has simple steps, low raw material cost and mild conditions, and is beneficial to mass production.
The third purpose of the invention is to provide an application of the clay mineral loaded molybdenum disulfide composite material, which is used as a heavy metal adsorption material for repairing heavy metal polluted water, and has high adsorption efficiency and large capacity on heavy metal in heavy metal polluted water solution.
In order to achieve the technical aim, the invention provides a clay mineral loaded molybdenum disulfide composite material, which is formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier.
The clay mineral loaded molybdenum disulfide composite material provided by the invention is formed by compounding active ingredient molybdenum disulfide and a clay mineral carrier, and has good adsorption performance on heavy metals based on the synergy between the ingredients and a special structure. The heavy metal adsorption active ingredient molybdenum disulfide two-dimensional nano-sheet is assembled into a micron-sized structure, the structural stability is good, the exposure of active sites is high, the adsorption effect of the heavy metal adsorption active ingredient molybdenum disulfide two-dimensional nano-sheet on the heavy metal is greatly improved, the clay mineral has rich pore structures and large specific surface area, the heavy metal adsorption active ingredient molybdenum disulfide two-dimensional nano-sheet has high physical adsorption performance, the pore structures and the high specific surface area of the clay mineral are utilized to provide attachment sites for the molybdenum disulfide active ingredient, the high dispersion of the molybdenum disulfide active ingredient is realized, and the reduction of the adsorption performance of the heavy metal caused by the agglomeration of the molybdenum disulfide active ingredient is prevented.
As a preferable scheme, the flower-shaped molybdenum disulfide microspheres are assembled by molybdenum disulfide nanosheets, and the particle size of the flower-shaped molybdenum disulfide microspheres is 2.5-3.5 mu m. The molybdenum disulfide nanosheets are of a nano structure and have high reactivity, and the nanosheets are assembled into a flower-shaped structure, so that an interlayer or pore structure is constructed, active sites are greatly exposed, and the reactivity is improved.
As a preferred embodiment, the clay mineral carrier is at least one of bentonite, diatomaceous earth, kaolin, sepiolite. The preferred clay minerals are lamellar or fluffy structures that provide attachment points for the molybdenum disulfide active ingredient loading.
As a preferable scheme, the mass ratio of the flower-shaped molybdenum disulfide microspheres to the clay mineral is 1:5-4:5. When the proportion of the flower-shaped molybdenum disulfide microspheres is too small, the chemical adsorption active sites of the composite material for heavy metals are too small, and when the proportion of the flower-shaped molybdenum disulfide microspheres is too high, the dispersibility of the molybdenum disulfide active ingredients is easy to be poor, so that the utilization rate of the molybdenum disulfide active ingredients is low.
The invention also provides a preparation method of the clay mineral loaded molybdenum disulfide composite material, which comprises the following steps of:
Scheme a: carrying out hydrothermal reaction on a molybdenum source, a sulfur source and clay minerals in an aqueous medium to obtain the catalyst;
Scheme B: and (3) carrying out hydrothermal reaction on a molybdenum source and a sulfur source in an aqueous medium, dispersing the obtained hydrothermal reaction product in water, and then adding clay mineral for heating and stirring reaction to obtain the catalyst.
The clay mineral loaded molybdenum disulfide composite material is mainly obtained through hydrothermal reaction, and in the scheme A, through one-step hydrothermal reaction, not only is the synthesis of flower-shaped molybdenum disulfide microspheres realized, but also the chemical bonding of the flower-shaped molybdenum disulfide microspheres and clay minerals is realized, and the in-situ loading is realized. In the scheme B, the synthesis of flower-shaped molybdenum disulfide microspheres is realized through two steps of reactions of hydrothermal reaction and conventional heating reaction, the first step of hydrothermal reaction mainly comprises the step of carrying the flower-shaped molybdenum disulfide microspheres on the surface of clay minerals in situ through chemical bonding, the two schemes can realize the synthesis of the clay mineral loaded molybdenum disulfide composite material, and the synthesized clay mineral loaded molybdenum disulfide composite material has good crystal structure morphology of molybdenum disulfide active components, high reactivity, good loading stability on the clay minerals and high dispersity, so that the composite material shows higher activity of adsorbing heavy metals.
The reaction principle in the scheme A of the invention is as follows: the sulfur source can be used as a reducing agent under a hydrothermal condition, hexavalent molybdenum is reduced to tetravalent molybdenum and molybdenum disulfide is generated, the molybdenum disulfide grows into a two-dimensional nano sheet structure under high temperature and high pressure, the two-dimensional nano sheet structure is assembled into a special flower-shaped microsphere structure, and in-situ load is realized by chemical bonding of sulfide anions of the molybdenum disulfide and metal ions in clay minerals; the key of the technology is that: the molybdenum source and the sulfur source solution are mixed with clay mineral, the molybdenum source and the sulfur source are dispersedly bonded on the surface of the clay mineral, and then the molybdenum disulfide generated by hydrothermal reduction reaction can directly realize load on the surface and pore structure of the clay mineral.
The reaction principle in the scheme B of the invention is as follows: the sulfur source can be used as a reducing agent under hydrothermal conditions, hexavalent molybdenum is reduced to tetravalent molybdenum and molybdenum disulfide is generated, the molybdenum disulfide grows into a two-dimensional nano sheet structure under high temperature and high pressure, the two-dimensional nano sheet structure is assembled into a special flower-shaped microsphere structure, and then the molybdenum disulfide material and clay mineral are heated and stirred to realize chemical bonding of the two materials.
As a preferred embodiment, in embodiment a or embodiment B: the molybdenum source is sodium molybdate dihydrate and/or ammonium molybdate tetrahydrate; the sulfur source is thiourea and/or thioacetamide. Both of these molybdenum and sulfur sources are common synthetic raw materials for molybdenum disulfide in the prior art.
In a preferred embodiment, in the embodiment a, the clay mineral is at least one of bentonite, diatomaceous earth, and kaolin. The preferred clay mineral has a mesoporous structure, and a large number of experiments show that the mesoporous structure is favorable for inducing uniform nucleation of molybdenum disulfide on the surface of the clay mineral and improving the purity of crystalline phases, so that flower-shaped molybdenum disulfide microspheres with better structural morphology are obtained, and the load stability is improved.
In a preferred embodiment, in the embodiment B, the clay mineral is at least one of bentonite and sepiolite.
As a preferred embodiment, in embodiment a or embodiment B: the molar ratio of the molybdenum source to the sulfur source is 1:3-1:6.
As a preferred embodiment, in the embodiment a, the clay mineral is 0.5 to 5 times the mass of the molybdenum source.
As a preferred embodiment, in the embodiment B, the clay mineral is 10 to 500% by mass of the hydrothermal reaction product. The clay mineral mass is more preferably 300-400% of the mass of the hydrothermal reaction product.
As a preferable scheme, in the scheme A, the temperature of the hydrothermal reaction is 160-260 ℃, the pH value is 3-5, and the reaction time is 12-36 h. In the hydrothermal reaction process, the special flower-shaped microsphere structure morphology molybdenum disulfide assembled by the molybdenum disulfide nanosheets is formed, chemical bonding between the molybdenum disulfide and clay minerals is realized, in-situ loading is realized, and loading stability is greatly improved. Further preferred hydrothermal reaction conditions: the temperature is 180-220 ℃ and the time is 20-28 h.
As a preferable scheme, in the scheme B, the temperature of the hydrothermal reaction is 160-260 ℃, the pH value is 3-5, and the reaction time is 12-36 h. In a preferred embodiment, in the embodiment B, the temperature of the heating and stirring is 25 to 65 ℃ and the time is 1 to 24 hours. In the hydrothermal reaction process, the special flower-shaped microsphere structural morphology molybdenum disulfide assembled by the molybdenum disulfide nanosheets is mainly formed, and the chemical bonding between the molybdenum disulfide and clay minerals is further realized through the heating reaction, so that in-situ loading is realized, and the loading stability is greatly improved. In a preferable pH environment, the specific surface area of clay mineral can be increased, so that the composite material with developed pores and higher specific surface area can be obtained. Further preferably, the temperature of the heating and stirring reaction is 25-35 ℃ and the time is 8-12 h.
The invention also provides application of the clay mineral loaded molybdenum disulfide composite material as a heavy metal adsorption material for repairing heavy metal polluted water.
As a preferable scheme, the clay mineral loaded molybdenum disulfide composite material is used for adsorbing Cd 2+ in heavy metal polluted water.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the clay mineral loaded molybdenum disulfide composite material provided by the invention is formed by compounding active ingredient molybdenum disulfide and a clay mineral carrier, and has good adsorption performance on heavy metals based on the synergy between the ingredients and a special structure. The heavy metal adsorption molybdenum disulfide active ingredient is assembled into a micron-sized structure by the two-dimensional nano sheet, the structural stability is good, the exposure of active sites is much, the adsorption effect of the heavy metal adsorption molybdenum disulfide active ingredient on the heavy metal is greatly improved, the clay mineral has rich pore structures and large specific surface area, the heavy metal adsorption molybdenum disulfide active ingredient has high physical adsorption performance, and the high dispersion of the heavy metal adsorption molybdenum disulfide active ingredient is realized by utilizing the pore structures and the high specific surface area of the clay mineral and providing the adhesion sites for the molybdenum disulfide active ingredient, so that the reduction of the adsorption performance of the heavy metal caused by the agglomeration of the molybdenum disulfide active ingredient is prevented.
The clay mineral loaded molybdenum disulfide composite material provided by the invention has good structural stability, a more developed pore structure, more heavy metal adsorption active sites and a better adsorption effect on heavy metals in heavy metal polluted water, and provides a foundation and reference for realizing heavy metal polluted water.
The clay mineral loaded molybdenum disulfide composite material provided by the invention has the advantages of simple preparation method, low raw material cost and mild conditions, and is beneficial to large-scale production.
Drawings
Fig. 1 is an X-ray diffraction pattern of the bentonite-based composite of example 2.
Fig. 2 is a scanning electron microscope image of the bentonite-based composite in example 2.
Fig. 3 is a transmission electron microscope image of the bentonite-based composite in example 2.
FIG. 4 is a drawing of Cd 2+ in the bentonite-based composite of example 8.
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
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 0.57g of thiourea, 0.3025g of sepiolite and 40ml of deionized water were added, after stirring uniformly, a dilute hydrochloric acid solution of 0.1mol/L was added dropwise to adjust ph=3, poured into a hydrothermal reaction vessel, and heated to 160 ℃ at a rate of 1 ℃/min, and kept for 16 hours. After the reaction is finished, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, the mixture is washed for 3 times by absolute ethyl alcohol and deionized water respectively, then the mixture is dried for 24 hours in vacuum, and the mixture is collected after grinding, thus obtaining the sepiolite-based composite material. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 62.35mg/L.
Example 2
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 1.14g of thiourea, 3.025g of bentonite and 40ml of deionized water are added, after stirring uniformly, a dilute hydrochloric acid solution of 0.1mol/L is added dropwise to adjust pH to be=5, the mixture is poured into a hydrothermal reaction kettle, the temperature is raised to 260 ℃ at a rate of 10 ℃/min, and the temperature is kept for 36 hours. After the reaction is finished, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, the black solid is respectively washed for 3 times by absolute ethyl alcohol and deionized water, then the vacuum drying is carried out for 24 hours, the bentonite-based composite material is obtained after grinding and collection, and an X-ray diffraction pattern and a scanning electron microscope pattern of the prepared material are shown in figures 1 and 2. In the XRD pattern of FIG. 1, peaks of molybdenum disulfide, silica and montmorillonite are simultaneously present, and montmorillonite is a main phase of bentonite, and silica is a main constituent substance of bentonite. In the scanning electron microscope picture of fig. 2, bentonite is mainly stacked in a block shape, part of spherical molybdenum disulfide is embedded in the bentonite, the molybdenum disulfide in the enlarged view is in a sheet-shaped structure, and in the transmission electron microscope picture of fig. 3, molybdenum disulfide grains and main component silicon dioxide of carrier bentonite form a typical heterostructure, which can be shown to be chemically bonded. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 52.88mg/L.
Example 3
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 0.76g of thiourea, 1.50g of bentonite and 40ml of deionized water are added, after stirring uniformly, a dilute hydrochloric acid solution of 0.1mol/L is added dropwise to adjust pH to be=5, and the mixture is poured into a hydrothermal reaction kettle, heated to 200 ℃ at a speed of 5 ℃/min, and kept for 24 hours. After the reaction is finished, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, and is respectively washed for 3 times by absolute ethyl alcohol and deionized water, then vacuum drying is carried out for 24 hours, and the bentonite-based composite material is obtained after grinding and collecting. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 75.33mg/L.
Example 4 (comparative example)
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 0.76g of thiourea, 1.50g of bentonite and 40ml of deionized water were added, after stirring uniformly, the pH=7 was adjusted, poured into a hydrothermal reaction kettle, heated to 200℃at a rate of 5℃per minute, and kept for 24 hours. After the reaction, the liquid is light yellow, and the product is black solid. Since the liquid environment is neutral, molybdenum disulfide is difficult to form, and thus bentonite-based composite materials cannot be obtained.
Example 5
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 0.57g of thiourea and 40ml of deionized water are added, after uniform stirring, 0.1mol/L of dilute hydrochloric acid solution is added dropwise to adjust pH to be 3, and the mixture is poured into a hydrothermal reaction kettle, heated to 160 ℃ at a speed of 1 ℃/min, and kept for 16 hours. After the reaction, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, washed 3 times by absolute ethyl alcohol and deionized water respectively, dried in vacuum for 24 hours, and ground and collected. Then the prepared material is dispersed in water solution by ultrasonic, added with 0.04g of sepiolite, heated to 25 ℃ and stirred for 1h, thus obtaining the sepiolite-based composite material. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 50.76mg/L.
Example 6
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 1.14g of thiourea and 40ml of deionized water are added, after uniform stirring, 0.1mol/L of dilute hydrochloric acid solution is added dropwise to adjust pH to be=5, and the mixture is poured into a hydrothermal reaction kettle, heated to 260 ℃ at a speed of 10 ℃/min, and kept for 36 hours. After the reaction, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, washed 3 times by absolute ethyl alcohol and deionized water respectively, dried in vacuum for 24 hours, and ground and collected. And then dispersing the prepared material in water solution by ultrasonic, adding 2g of bentonite, heating to 65 ℃, and stirring for 24 hours to obtain the bentonite-based composite material. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 45.38mg/L.
Example 7
In a 50ml beaker, 0.605g of sodium molybdate dihydrate, 0.76g of thiourea and 40ml of deionized water are added, after uniform stirring, 0.1mol/L of dilute hydrochloric acid solution is added dropwise to adjust pH to be 4, and the mixture is poured into a hydrothermal reaction kettle, heated to 200 ℃ at a speed of 5 ℃/min, and kept for 24 hours. After the reaction, the liquid is colorless and transparent, the product is black solid, the black solid is taken out, washed 3 times by absolute ethyl alcohol and deionized water respectively, dried in vacuum for 24 hours, and ground and collected. Then the prepared material is dispersed in water solution by ultrasonic, 1.5g of bentonite is added, then the mixture is heated to 35 ℃ and stirred for 12 hours, and the bentonite-based composite material is obtained. The prepared composite material is applied to removing Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of the Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, and the maximum adsorption capacity at the time of balancing is 57.26mg/L.
Example 8
The composite material prepared in the example 3 is applied to the adsorption of Cd 2+ in an aqueous solution, the solid-to-liquid ratio is 1.5g/L, the concentration of Cd 2+ solution is 200mg/L, the temperature is 25 ℃, the pH=6, the adsorption result of the material is shown in figure 3, the adsorption capacity is obviously improved along with the change of time when the adsorption capacity is 0-75 min, the adsorption capacity tends to be stable after 75min, and the maximum adsorption capacity is 75.33mg/L.
Claims (3)
1. The application of the clay mineral loaded molybdenum disulfide composite material is characterized in that: the clay mineral loaded molybdenum disulfide composite material is used for adsorbing Cd 2+ in a heavy metal polluted water body;
The clay mineral loaded molybdenum disulfide composite material is formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier; the flower-shaped molybdenum disulfide microspheres are assembled by molybdenum disulfide nanosheets, and the particle size of the flower-shaped molybdenum disulfide microspheres is 2.5-3.5 mu m; the clay mineral carrier is at least one of bentonite, diatomite and kaolin;
The clay mineral loaded molybdenum disulfide composite material is prepared by the following method: carrying out hydrothermal reaction on a molybdenum source, a sulfur source and clay minerals in an aqueous medium to obtain the catalyst; the temperature of the hydrothermal reaction is 160-260 ℃, the pH value is 3-5, and the reaction time is 12-36 h; the mol ratio of the molybdenum source to the sulfur source is 1:3-1:6;
the mass of the clay mineral is 0.5-5 times of the mass of the molybdenum source.
2. The use of a clay mineral supported molybdenum disulfide composite according to claim 1, characterized in that: the mass ratio of the flower-shaped molybdenum disulfide microspheres to clay mineral is 1:5-4:5.
3. The use of a clay mineral supported molybdenum disulfide composite according to claim 1, characterized in that:
the molybdenum source is sodium molybdate dihydrate and/or ammonium molybdate tetrahydrate;
the sulfur source is thiourea and/or thioacetamide.
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