CN114259981A - 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 72
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 29
- 239000004005 microsphere Substances 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 25
- 239000000440 bentonite Substances 0.000 claims description 24
- 229910000278 bentonite Inorganic materials 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 239000004113 Sepiolite Substances 0.000 claims description 8
- 229910052624 sepiolite Inorganic materials 0.000 claims description 8
- 235000019355 sepiolite Nutrition 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 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 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 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 37
- 239000004480 active ingredient Substances 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 20
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- 239000000243 solution Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 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
- 239000011651 chromium Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
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- 239000010410 layer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- -1 transition metal disulfide Chemical class 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- 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
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 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
- 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
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 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 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 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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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 clay mineral with developed pores and high specific surface area is used as the carrier, and the heavy metal adsorption active ingredient molybdenum disulfide active nanosheets are assembled into the flower-shaped microspheres.
Description
Technical Field
The invention relates to an adsorption material, in particular to a clay mineral loaded molybdenum disulfide composite material, a preparation method and application thereof in the aspect of heavy metal polluted water body remediation, belonging to the field of environmental functional materials,
background
Molybdenum disulfide is a typical layered transition metal disulfide, each layer is composed of two sulfur sheets and a built-in molybdenum sheet, the molybdenum disulfide is similar to a sandwich structure, the layers are connected with each other through Van der Waals force, the molybdenum disulfide is easy to separate due to different stacking modes, and the molybdenum disulfide has three crystal forms of 1T, 2H and 3R and is the most stable in property in molybdenum sulfides. Common preparation methods are mechanical stripping, liquid stripping, chemical stripping, electrochemical stripping, chemical vapor deposition and hydrothermal synthesis. The former four methods are to peel off massive molybdenum disulfide to prepare molybdenum disulfide nanosheets by decomposing weak van der waals force between layers, and the latter method is to synthesize molybdenum disulfide nanosheets by utilizing a molybdenum source and a sulfur source. Molybdenum disulfide is a typical n-type semiconductor, has a unique electronic band structure and has excellent photocatalytic performance. As a two-dimensional material, the molybdenum disulfide with larger interlayer spacing shows excellent electrochemical performance and is widely used in lithium ion battery storage energy sources. In addition, the method has wide application in the fields of field effect transistors, sensors, photodetectors, adsorption and the like.
Due to the unique two-dimensional structure, the molybdenum disulfide has a huge specific surface area, and since 2010, the two-dimensional molybdenum disulfide has become one of the most popular adsorbents, and sulfur atoms are exposed to the outside, so that the molybdenum disulfide has better adsorption capacity on metals. Liu and the like adopt ultrasonic liquid phase auxiliary stripping and hydro-thermal synthesis to prepare two types of molybdenum disulfide nanosheets, and Pb in different shapes is explored2+The result shows that the adsorption effect on Pb is achieved under the condition of low concentration (60mg/L)2+The removal rates are respectively 98.4 percent and 20.6 percent, and the adsorption quantity of the hydrothermally synthesized molybdenum disulfide can reach 174.2mg/g (roll of structural characteristics of MoS)2nanosheets on Pb2+removal in aqueous solution”,LIU,Y,et al.,Environmental Technology&Innovation,2021,22 (14-15): 101385). Chen isostructural bond disulfideThe molybdenum/lignin composite material is used for removing Cr (VI) in a water environment, has a remarkable effect of removing Cr (VI) when the pH value is 2, the T value is 298.15k and the concentration is 20mg/L, has an adsorption capacity of 198.70mg/g, and can remove 99.35 Cr (VI) within 30min2/A magnesium-derived Carbon Nanocomposites for high efficiency Efficient Removal of Cr (VI) from Aqueous Environment ", CHEN, H, et al, Journal of Hazardous Materials,2020,408(49): 124847). Paul et al cysteine functionalized molybdenum disulfide for removing Cd from water2+The result shows that the Cd can be absorbed by 76 +/-15 mg/g2+(“Few-layer molybdenum disulfide nanosheets functionalized with L-cysteine for selective capture of Cd2+ions ", BAZYLEWSKI, P, et al, Flatchem,2018,11: 15-23). Molybdenum disulfide prepared by a hydrothermal method is loaded on carbon aerogel by GuoQinming of Zhejiang university of science and technology, is used for removing Cr (VI) in water, has the removal capacity of 460.2mg/g, and has excellent reusability (' CA/MoS)2Preparation of the composite and its hexavalent chromium removal performance ", Guoqinming et al, 2021,45(02): 212-220). The molybdenum disulfide is prepared by a molten salt method in the Stevensis et al, and then the molybdenum disulfide is compounded with silver phosphate, and the prepared material can absorb the iodide ions up to 628.93mg/g (experimental study on the adsorption performance of silver phosphate/molybdenum disulfide on the iodide ions, Bell et al, hydrometallurgy, 2019,38(06): 476-. Although molybdenum disulfide is frequently used for removing metal ions, the shape of the commonly prepared molybdenum disulfide is difficult to regulate and control, the dispersibility is poor, the molybdenum disulfide is limited by the cost, and the molybdenum disulfide is not widely applied compared with traditional adsorbents such as activated carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a composite material formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier, the composite material takes a clay mineral with developed pores and high specific surface area as the carrier, and heavy metal adsorption active ingredient molybdenum disulfide nanosheets are assembled into the flower-shaped microspheres, so that the flower-shaped microspheres have stable structural morphology, are highly dispersed on the carrier, are highly exposed at active sites, and show good adsorption performance on heavy metals.
The second purpose of the invention is to provide a method for preparing the clay mineral loaded molybdenum disulfide composite material, which has the advantages of simple steps, low raw material cost and mild conditions, and is beneficial to large-scale production.
The third purpose of the invention is to provide an application of the clay mineral loaded molybdenum disulfide composite material, wherein the clay mineral loaded molybdenum disulfide composite material is used as a heavy metal adsorption material for repairing heavy metal polluted water, and has high adsorption efficiency and large capacity for heavy metals in heavy metal polluted water solution.
In order to achieve the technical purpose, 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 compounded by active ingredient molybdenum disulfide and a clay mineral carrier, and shows better adsorption performance to heavy metals based on the synergy between the ingredients and the special structure of the two. The two-dimensional nanosheet of the heavy metal adsorption active ingredient molybdenum disulfide is assembled into a micron-shaped structure, the structural stability is good, active sites are exposed more, the adsorption effect of the two-dimensional nanosheet on heavy metal is greatly improved, the clay mineral has an abundant pore structure and a larger specific surface area, the heavy metal has higher physical adsorption performance, attachment sites are provided for the molybdenum disulfide active ingredient by utilizing the pore structure and the high specific surface area of the clay mineral, the high dispersion of the molybdenum disulfide active ingredient is realized, and the reduction of the adsorption performance on 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 microns. The molybdenum disulfide nanosheet is of a nanostructure and has high reaction activity, and the nanosheet is assembled into a flower-shaped structure to construct an interlayer or pore structure, so that active sites are greatly exposed, and the reaction activity is improved.
As a preferred scheme, the clay mineral carrier is at least one of bentonite, diatomite, kaolin and sepiolite. Preferred clay minerals are layered or fluffy structures that provide attachment points for molybdenum disulfide active loading.
As a preferable scheme, the mass ratio of the flower-shaped molybdenum disulfide microspheres to the clay mineral is 1: 5-4: 5. 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 the proportion of the flower-shaped molybdenum disulfide microspheres is too high, so that the dispersibility of the molybdenum disulfide active ingredients is poor, and 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 is prepared by the following scheme A or scheme B:
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: carrying out hydrothermal reaction on a molybdenum source and a sulfur source in an aqueous medium, dispersing the obtained hydrothermal reaction product in water, adding clay minerals, heating and stirring for reaction, and obtaining the catalyst.
The clay mineral loaded molybdenum disulfide composite material is mainly obtained through a hydrothermal reaction, and in the scheme A, through one-step hydrothermal reaction, the synthesis of flower-shaped molybdenum disulfide microspheres is realized, the chemical bonding of the flower-shaped molybdenum disulfide microspheres and clay minerals is realized, and the in-situ loading is realized. The method is realized through hydrothermal reaction and conventional heating reaction two-step reaction in a scheme B, the first step of hydrothermal reaction mainly realizes the synthesis of flower-shaped molybdenum disulfide microspheres, the second step of heating reaction loads the flower-shaped molybdenum disulfide microspheres on the surface of clay minerals through chemical bonding in-situ, the synthesis of the clay mineral load molybdenum disulfide composite material can be realized through the two schemes, the crystal structure and the appearance of molybdenum disulfide active ingredients in the synthesized clay mineral load molybdenum disulfide composite material are good, the reaction activity is high, the load stability on the clay minerals is good, the dispersity is high, and the composite material can show higher activity of adsorbing heavy metals.
The reaction principle in scheme A of the invention is as follows: the sulfur source can be used as a reducing agent under the hydrothermal condition, hexavalent molybdenum is reduced into tetravalent molybdenum, molybdenum disulfide is generated, the molybdenum disulfide grows into a two-dimensional nano flaky structure under high temperature and high pressure, the two-dimensional nano flaky structure is assembled into a special flower-shaped microsphere structure, and sulfur negative ions of the molybdenum disulfide and metal ions in clay minerals are chemically bonded to realize in-situ loading; the key point of the technology is that: the molybdenum source and the sulfur source are mixed with the clay mineral, the molybdenum source and the sulfur source are dispersedly bonded on the surface of the clay mineral, and then molybdenum disulfide generated through hydrothermal reduction reaction can directly realize loading on the surface and the pore structure of the clay mineral.
The reaction principle in scheme B of the invention is as follows: the sulfur source can be used as a reducing agent under the hydrothermal condition, hexavalent molybdenum is reduced into tetravalent molybdenum, molybdenum disulfide is generated, the molybdenum disulfide grows into a two-dimensional nano flaky structure under high temperature and high pressure, the two-dimensional nano flaky structure is assembled into a special flower-shaped microsphere structure, and the molybdenum disulfide material and clay minerals are heated and stirred to realize chemical bonding of the two materials.
As a preferred embodiment, in the embodiment a or the embodiment B: the molybdenum source is sodium molybdate dihydrate and/or ammonium molybdate tetrahydrate; the sulfur source is thiourea and/or thioacetamide. These molybdenum and sulfur sources are common raw materials for the synthesis of molybdenum disulfide in the prior art.
In a preferred embodiment, in the embodiment a, the clay mineral is at least one of bentonite, diatomite, and kaolin. The optimized clay mineral has a mesoporous structure, and a large number of experiments find that the mesoporous structure is beneficial to inducing the molybdenum disulfide to uniformly nucleate on the surface of the clay mineral and improving the purity of a crystal phase, so that flower-shaped molybdenum disulfide microspheres with better structural morphology can be 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 the embodiment a or the embodiment B: the molar ratio of the molybdenum source to the sulfur source is 1: 3-1: 6.
As a preferable scheme, in the scheme a, the mass of the clay mineral is 0.5 to 5 times of the mass of the molybdenum source.
As a preferable scheme, in the scheme B, the mass of the clay mineral is 10 to 500% of the mass of the hydrothermal reaction product. The mass of the clay mineral is more preferably 300-400% of the mass of the hydrothermal reaction product.
In 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 molybdenum disulfide with a flower-like microsphere structure morphology formed by assembling molybdenum disulfide nanosheets is formed, chemical bonding between the molybdenum disulfide and clay minerals is realized, in-situ loading is realized, and the loading stability is greatly improved. Further preferred hydrothermal reaction conditions: the temperature is 180-220 ℃, and the time is 20-28 h.
In 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 preferable scheme, in the scheme B, the heating and stirring temperature is 25-65 ℃ and the time is 1-24 h. In the hydrothermal reaction process, special molybdenum disulfide with a flower-like microsphere structure morphology and assembled by molybdenum disulfide nanosheets is mainly formed, chemical bonding between the molybdenum disulfide and clay minerals is further realized through heating reaction, in-situ loading is realized, and the loading stability is greatly improved. Under the preferable pH environment, the specific surface area of the clay mineral can be increased, so that the composite material with developed pores and higher specific surface area is obtained. The further preferable temperature for heating and stirring reaction is 25-35 ℃, and the time is 8-12 h.
The invention also provides an application of the clay mineral loaded molybdenum disulfide composite material as a heavy metal adsorption material for repairing heavy metal polluted water.
As an optimal scheme, the clay mineral loaded molybdenum disulfide composite material is used for Cd in heavy metal polluted water body2+Adsorption of (3).
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the clay mineral loaded molybdenum disulfide composite material provided by the invention is compounded by active ingredient molybdenum disulfide and a clay mineral carrier, and shows better adsorption performance to heavy metals based on the synergy between the ingredients and the special structure of the two. Heavy metal adsorbs molybdenum disulfide active ingredient and assembles into micron form structure by two-dimensional nanosheet, structural stability is good, and the active site exposes much, improved its adsorption to heavy metal greatly, and clay mineral itself has abundant pore structure and great specific surface area, has higher physical adsorption performance to heavy metal, and utilize clay mineral's pore structure and high specific surface and provide the attachment site for molybdenum disulfide active ingredient, realize its high dispersion, prevent that molybdenum disulfide active ingredient's reunion and lead to the decline to heavy metal adsorption performance.
The clay mineral loaded molybdenum disulfide composite material provided by the invention has the advantages of good structural stability, developed pore structure, more heavy metal adsorption active sites, and good 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 is simple in preparation method, low in raw material cost, mild in condition and beneficial to large-scale production.
Drawings
FIG. 1 is an X-ray diffraction chart of a bentonite-based composite material in example 2.
Fig. 2 is a scanning electron micrograph of the bentonite-based composite material of example 2.
FIG. 3 is a transmission electron micrograph of a bentonite-based composite material in example 2.
FIG. 4 is Cd pair of the bentonite-based composite material in example 82+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 0.605g of sodium molybdate dihydrate, 0.57g of thiourea, 0.3025g of sepiolite and 40ml of deionized water into a 50ml beaker, uniformly stirring, dropwise adding 0.1mol/L of dilute hydrochloric acid solution to adjust the pH value to 3, pouring into a hydrothermal reaction kettle, heating to 160 ℃ at the speed of 1 ℃/min, and preserving heat for 16 h. And after the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is respectively washed for 3 times by absolute ethyl alcohol and deionized water, and then the product is dried for 24 hours in vacuum, and is collected after being ground, so that the sepiolite-based composite material is obtained. The prepared composite material is applied to removing Cd in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 62.35 mg/L.
Example 2
Adding 0.605g of sodium molybdate dihydrate, 1.14g of thiourea, 3.025g of bentonite and 40ml of deionized water into a 50ml beaker, uniformly stirring, dropwise adding 0.1mol/L of dilute hydrochloric acid solution to adjust the pH value to 5, pouring into a hydrothermal reaction kettle, heating to 260 ℃ at the speed of 10 ℃/min, and preserving heat for 36 hours. After the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is washed for 3 times by absolute ethyl alcohol and deionized water respectively, then the product is dried for 24 hours in vacuum, and the product is collected after being ground, so that the bentonite-based composite material is obtained, and the X-ray diffraction pattern and the 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, which is the main phase of bentonite, appear simultaneously, and silica is the main constituent of bentonite. In the picture of a scanning electron microscope of fig. 2, bentonite is mainly stacked in a block shape, part of spherical molybdenum disulfide is embedded in the bentonite, in the enlarged picture, the molybdenum disulfide is in a sheet structure, and in the picture of a transmission electron microscope of fig. 3, molybdenum disulfide grains and silicon dioxide which is a main component of the carrier bentonite form a typical heterostructure and can show chemical bonding. The prepared composite material is applied to removing Cd in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 52.88 mg/L.
Example 3
Burning in 50ml0.605g of sodium molybdate dihydrate, 0.76g of thiourea, 1.50g of bentonite and 40ml of deionized water are added into a cup, after the mixture is uniformly stirred, 0.1mol/L of dilute hydrochloric acid solution is added dropwise to adjust the pH value to be 5, the mixture is poured into a hydrothermal reaction kettle, the temperature is raised to 200 ℃ at the speed of 5 ℃/min, and the temperature is kept for 24 hours. And after the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is respectively washed for 3 times by absolute ethyl alcohol and deionized water, and then the product is dried for 24 hours in vacuum, ground and collected, so that the bentonite-based composite material is obtained. The prepared composite material is applied to removing Cd in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 75.33 mg/L.
Example 4 (comparative example)
Adding 0.605g of sodium molybdate dihydrate, 0.76g of thiourea, 1.50g of bentonite and 40ml of deionized water into a 50ml beaker, uniformly stirring, adjusting the pH value to 7, pouring into a hydrothermal reaction kettle, raising the temperature to 200 ℃ at the speed of 5 ℃/min, and preserving the temperature for 24 h. After the reaction was complete, the liquid was pale yellow and the product was a black solid. Because the liquid environment is neutral, molybdenum disulfide is difficult to form, so that the bentonite-based composite material cannot be obtained.
Example 5
Adding 0.605g of sodium molybdate dihydrate, 0.57g of thiourea and 40ml of deionized water into a 50ml beaker, uniformly stirring, dropwise adding 0.1mol/L of dilute hydrochloric acid solution to adjust the pH value to 3, pouring into a hydrothermal reaction kettle, heating to 160 ℃ at the speed of 1 ℃/min, and preserving heat for 16 h. After the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is respectively washed for 3 times by absolute ethyl alcohol and deionized water, and then the product is dried for 24 hours in vacuum, and is collected after being ground. And then ultrasonically dispersing the prepared material in an aqueous solution, adding 0.04g of sepiolite, heating to 25 ℃, and stirring for 1h to obtain the sepiolite-based composite material. The prepared composite material is applied to removing Cd in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 50.76 mg/L.
Example 6
In a 50ml beaker,adding 0.605g of sodium molybdate dihydrate, 1.14g of thiourea and 40ml of deionized water, stirring uniformly, dropwise adding 0.1mol/L dilute hydrochloric acid solution to adjust the pH value to 5, pouring into a hydrothermal reaction kettle, heating to 260 ℃ at the speed of 10 ℃/min, and preserving heat for 36 h. After the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is respectively washed for 3 times by absolute ethyl alcohol and deionized water, and then the product is dried for 24 hours in vacuum, and is collected after being ground. Then ultrasonically dispersing the prepared material in an aqueous solution, 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 in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 45.38 mg/L.
Example 7
Adding 0.605g of sodium molybdate dihydrate, 0.76g of thiourea and 40ml of deionized water into a 50ml beaker, uniformly stirring, dropwise adding 0.1mol/L of dilute hydrochloric acid solution to adjust the pH value to 4, pouring into a hydrothermal reaction kettle, raising the temperature to 200 ℃ at the speed of 5 ℃/min, and preserving the temperature for 24 h. After the reaction is finished, the liquid is colorless and transparent, the product is a black solid, the black solid is taken out, the product is respectively washed for 3 times by absolute ethyl alcohol and deionized water, and then the product is dried for 24 hours in vacuum, and is collected after being ground. 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, thus obtaining the bentonite-based composite material. The prepared composite material is applied to removing Cd in aqueous solution2+The solid-liquid ratio is 1.5g/L, Cd2+The solution concentration was 200mg/L, the temperature was 25 ℃, the pH was 6, and the maximum adsorption at equilibrium was 57.26 mg/L.
Example 8
The composite material prepared in the example 3 is applied to Cd in an aqueous solution2+Adsorption with a solid-to-liquid ratio of 1.5g/L and Cd2+The concentration of the solution is 200mg/L, the temperature is 25 ℃, the pH is 6, the adsorption result of the material is shown in figure 3, the adsorption quantity is obviously improved along with the change of time when the time is 0-75 min, the adsorption quantity tends to be stable after 75min, and the maximum adsorption quantity is 75.33 mg/L.
Claims (10)
1. The clay mineral loaded molybdenum disulfide composite material is characterized in that: is formed by loading flower-shaped molybdenum disulfide microspheres on a clay mineral carrier.
2. The clay mineral loaded molybdenum disulfide composite material as claimed in claim 1, wherein: the flower-shaped molybdenum disulfide microspheres are formed by assembling molybdenum disulfide nanosheets, and the particle size of the flower-shaped molybdenum disulfide microspheres is 2.5-3.5 microns.
3. The clay mineral loaded molybdenum disulfide composite material as claimed in claim 1, wherein: the clay mineral carrier is at least one of bentonite, diatomite, kaolin and sepiolite.
4. The clay mineral loaded molybdenum disulfide composite material according to any one of claims 1 to 3, wherein: the mass ratio of the flower-shaped molybdenum disulfide microspheres to the clay mineral is 1: 5-4: 5.
5. The method for preparing the clay mineral loaded molybdenum disulfide composite material as claimed in any one of claims 1 to 4, wherein: prepared by scheme a or scheme B:
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: carrying out hydrothermal reaction on a molybdenum source and a sulfur source in an aqueous medium, dispersing the obtained hydrothermal reaction product in water, adding clay minerals, heating and stirring for reaction, and obtaining the catalyst.
6. The method for preparing the clay mineral loaded molybdenum disulfide composite material according to claim 5, wherein:
in scheme a or scheme B:
the molybdenum source is sodium molybdate dihydrate and/or ammonium molybdate tetrahydrate;
the sulfur source is thiourea and/or thioacetamide;
in the case of the scheme A, the reaction,
the clay mineral is at least one of bentonite, diatomite and kaolin;
in the case of the embodiment B, the following steps are carried out,
the clay mineral is at least one of bentonite and sepiolite.
7. The method for preparing the clay mineral loaded molybdenum disulfide composite material according to claim 5, wherein:
in scheme a or scheme B:
the molar ratio of the molybdenum source to the sulfur source is 1: 3-1: 6;
in the case of the scheme A, the reaction,
the mass of the clay mineral is 0.5-5 times of that of the molybdenum source;
in the scheme B, the mass of the clay mineral is 10-500% of that of the hydrothermal reaction product.
8. The method for preparing the clay mineral loaded molybdenum disulfide composite material according to claim 5, wherein: 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.
9. The method for preparing the clay mineral loaded molybdenum disulfide composite material according to claim 5, wherein: 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; the heating and stirring temperature is 25-65 ℃, and the time is 1-24 hours.
10. The application of the clay mineral loaded molybdenum disulfide composite material as claimed in any one of claims 1 to 4, is characterized in that: the heavy metal adsorbing material is used for repairing heavy metal polluted water.
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