CN113457632A - Two-dimensional transition metal carbide/metal organic framework composite aerogel and preparation method thereof - Google Patents
Two-dimensional transition metal carbide/metal organic framework composite aerogel and preparation method thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 79
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 69
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 67
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 25
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 33
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 26
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 26
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- 229910019637 Nb2AlC Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 30
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- -1 transition metal carbides Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28047—Gels
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- 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
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Abstract
The invention provides a two-dimensional transition metal carbide/metal organic framework composite aerogel and a preparation method and application thereof. The method specifically comprises the following steps: and (3) etching and stripping the layered MAX phase powder by adopting lithium fluoride and hydrochloric acid solution to obtain the stable suspension of the two-dimensional transition metal carbide nanosheet. And adding a cross-linking agent into the suspension, guiding the suspension to self-assemble to form hydrogel, and performing vacuum freeze drying to obtain the two-dimensional transition metal carbide aerogel. And soaking the prepared two-dimensional transition metal carbide aerogel in a precursor solution of a metal organic framework material, forming the metal organic framework material in situ in a pore channel of the two-dimensional transition metal carbide aerogel, and finally forming the two-dimensional transition metal carbide/metal organic framework composite aerogel. The composite aerogel material prepared by the invention has high specific surface area, developed pores and high adsorption capacity to metal ions, and is an ideal adsorption material.
Description
Technical Field
The invention relates to a composite aerogel and a preparation method and application thereof, in particular to a two-dimensional transition metal carbide/metal organic framework composite aerogel and a preparation method and application thereof.
Background
With the rapid development of industry, the discharge of garbage presents an unprecedented challenge to the environment. The industrial waste contains a large amount of fatal heavy metal ions, which not only seriously pollutes the environment, but also causes secondary pollution to surface water and underground water, and poses great threat to human survival. Adsorption is a widely used technique for water treatment. In the field of adsorption, porous materials are considered to be a very useful adsorbent. Therefore, it is important to develop an adsorbent having excellent performance.
The transition metal carbide is a novel two-dimensional material, and has unique properties of layered morphology, adjustable surface chemical environment, different chemical composition forms and the like, so that the two-dimensional material has good metal conductivity, hydrophilicity and functional adjustability, and can be used for obtaining two-dimensional transition metal carbides with different properties by adjusting chemical components and changing surface functional groups according to different property requirements, so that the two-dimensional transition metal carbides can be applied to the fields of adsorption, energy storage, electrochemical sensing and the like. The metal organic framework material refers to a crystalline porous material with a periodic network structure formed by self-assembly of transition metal ions and organic ligands. They have the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like. Based on the properties, the material can be widely applied to the fields of water treatment, gas adsorption/separation, catalysis, sensing, energy storage and the like. Aerogel is a solid form, the least dense solid in the world. At present, no two-dimensional transition metal carbide/metal organic framework composite aerogel is reported. By combining the advantages of the two-dimensional transition metal carbide, the metal organic framework and the aerogel, the two-dimensional transition metal carbide/metal organic framework composite aerogel material with excellent adsorption performance is prepared.
Disclosure of Invention
Based on the above technical background, the present invention aims to provide a composite aerogel material applied to metal ion adsorption, and in particular to a preparation method of a two-dimensional transition metal carbide/metal organic framework composite aerogel applied to metal ion adsorption.
In order to realize one of the purposes of the invention, the following technical scheme is provided:
the preparation method of the two-dimensional transition metal carbide/metal organic framework composite aerogel comprises the following steps:
1) adding layered MAX-phase ceramic powder into a hydrochloric acid solution in which lithium fluoride is dissolved, and performing magnetic stirring reaction, wherein the mass ratio of MAX-phase ceramic powder to lithium fluoride is 0.5-2: washing a reaction product until the supernatant is nearly neutral to obtain a multilayer two-dimensional transition metal carbide, dispersing the obtained multilayer two-dimensional transition metal carbide in deionized water, ultrasonically stripping, and centrifuging to obtain a stable suspension of two-dimensional transition metal carbide nanosheets;
2) adjusting the concentration of the two-dimensional transition metal carbide suspension to 10-50 mg/mL, and adding a cross-linking agent into the suspension obtained in the step 1), wherein the mass ratio of the two-dimensional transition metal carbide to the cross-linking agent is 0.2-5: 1, guiding the hydrogel to be assembled to form hydrogel, and carrying out vacuum freeze drying to obtain a two-dimensional transition metal carbide aerogel material;
3) directly soaking the two-dimensional transition metal carbide aerogel prepared in the step 2) in a precursor solution of a metal organic framework material, reacting for a period of time at room temperature, washing, and freeze-drying to obtain the two-dimensional transition metal carbide/metal organic framework composite aerogel material, wherein the mass ratio of the two-dimensional transition metal carbide to the metal organic framework material is 0.5-2: 1.
preferably, the MAX phase ceramic in the step 1) is Ti3AlC2、Ti2AlC、Nb2AlC、V2AlC and Cr2One or more of AlC.
Preferably, the temperature of the magnetic stirring in the step 1) is 30-50 ℃, and the time of the magnetic stirring is 6-48 hours; the centrifugal rotating speed in the step 1) is 2000-6000 rpm, and the time of each centrifugation is 5-10 min.
Preferably, the cross-linking agent in the step 2) is one or two of diethylenetriamine, triethylene tetramine and tetraethylene pentamine; the vacuum freeze drying refers to pre-freezing for 0.5-6 h at the temperature of-20-196 ℃, and freeze drying for 6-48 h at the temperature of-45-40 ℃ and under the pressure of 2-50 Pa.
Preferably, the precursor solution of the metal organic framework material in the step 3) comprises a methanol solution of zinc nitrate and 2-methylimidazole for preparing ZIF-8, and a methanol solution of cobalt nitrate and 2-methylimidazole for preparing ZIF-67; the reaction time is 2-48 h; the freeze drying refers to pre-freezing for 0.5-6 h at the temperature of-20 ℃ to-196 ℃, and freeze drying for 6-48 h at the temperature of-45 ℃ to 40 ℃ and under the pressure of 2-50 Pa.
Preferably, the concentration of the zinc nitrate is 0.1-1.0M, the concentration of the cobalt nitrate is 0.1-1.0M, and the concentration of the 2-methylimidazole is 0.1-1.0M.
In order to achieve the second object of the invention, the following technical scheme is provided:
the two-dimensional transition metal carbide/metal organic framework composite aerogel material prepared by the method takes a three-dimensional network structure consisting of two-dimensional transition metal carbide sheet layers as a substrate, and the metal organic framework material is loaded on the two-dimensional transition metal carbide sheet layers,
the two-dimensional transition metal carbide is Ti3C2Tx、Ti2CTx、Nb2CTx、V2CTxAnd Cr2CTxOne or more of, TxIs one or the combination of-OH and-F,
the density of the composite aerogel is 0.06-0.8 g cm-3The specific surface area is 200-1500 m2 g-1。
In order to achieve the third object of the invention, the following technical scheme is provided:
the two-dimensional transition metal carbide/metal organic framework composite aerogel material is applied as a metal ion adsorption material.
Has the advantages that:
the preparation method of the two-dimensional transition metal carbide/metal organic framework composite aerogel material is simple and convenient to operate, low in cost and suitable for large-scale production.
The two-dimensional transition metal carbide/metal organic framework composite aerogel material provided by the invention has excellent performance in the field of metal ion adsorption.
In the present invention, the equipment, instruments, materials, processes, preparation conditions, etc., which are used are those conventionally used in the art or can be easily obtained according to the techniques conventionally used in the art, if not specifically mentioned.
Drawings
FIG. 1 shows Ti prepared in example 13C2TxScanning electron microscope photos of the/ZIF-8 composite aerogel;
FIG. 2 is Ti prepared in example 13C2TxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions is improved;
FIG. 3 shows Nb prepared in example 22CTxScanning electron microscope photos of the/ZIF-8 composite aerogel;
FIG. 4 shows Nb prepared in example 22CTxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions is improved;
FIG. 5 shows Ti prepared in example 33C2TxA scanning electron microscope photograph of the/ZIF-67 composite aerogel;
FIG. 6 is Ti prepared in example 33C2TxA nitrogen adsorption and desorption isotherm of the/ZIF-67 composite aerogel;
FIG. 7 shows Ti prepared in example 43C2TxScanning electron microscope photos of the/ZIF-8 composite aerogel;
FIG. 8 is Ti prepared in example 43C2TxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
1) 1.6g of lamellar MAX phase Ti3AlC2Adding ceramic powder into 20mL hydrochloric acid (9.0M) solution dissolved with 2.0g of lithium fluoride, magnetically stirring at 35 ℃ for reaction for 24h, washing the reaction product until the supernatant is nearly neutral, and obtaining multilayer two-dimensional transition metal carbide Ti3C2TxThe obtained multilayer two-dimensional transition metal carbide Ti3C2TxDispersing in deionized water, ultrasonically stripping, and centrifuging at 6000rpm for 10min to obtain two-dimensional transition metal carbide Ti3C2TxA stable suspension of nanoplatelets;
2) adjusting two-dimensional transition metal carbide Ti3C2TxThe concentration of the suspension is 20mg/mL, a cross-linking agent diethylenetriamine (40mg) is added into 10mL of the suspension obtained in the step 1) to guide the assembly to form hydrogel, the obtained hydrogel material is pre-frozen at the liquid nitrogen temperature of-196 ℃ for 0.5h, and then is subjected to vacuum freeze drying for 48h under the conditions that the temperature is 25 ℃ and the pressure is 10Pa to obtain Ti3C2TxAn aerogel material;
3) the obtained Ti3C2TxAerogel (200 mg) was immersed directly in 25mL of zinc nitrate (0.5M) in methanol and stirred at room temperature for 1h to promote the formation of zinc ions in the Ti3C2TxAdsorbing aerogel, adding 25mL of 2-methylimidazole (0.5M) methanol solution, reacting the mixture at room temperature for 24 hr, washing, vacuum filtering, pre-freezing at-196 deg.C liquid nitrogen temperature for 0.5 hr, and vacuum freeze-drying at 25 deg.C and 10Pa for 48 hr to obtain Ti3C2TxA ZIF-8 aerogel material.
For Ti obtained in example 13C2TxThe ZIF-8 composite aerogel carries out related experiments, and the results are as follows:
FIG. 1 shows the results of example 1Prepared Ti3C2TxScanning electron micrograph of/ZIF-8 composite aerogel, as can be seen from FIG. 1, Ti3C2Txthe/ZIF-8 composite aerogel has a rich porous structure.
FIG. 2 is Ti prepared in example 13C2TxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions can be seen from figure 2, and the prepared Ti3C2Txthe/ZIF-8 composite aerogel has better adsorption performance on mercury ions, and the adsorption performance reaches 175 mg/g.
Example 2
The main differences between this embodiment and the specific embodiment 1 are: the MAX phase is Nb2AlC。
1) 1.6g of lamellar MAX phase Nb2Adding AlC ceramic powder into 20mL hydrochloric acid (9.0M) solution dissolved with 2.0g of lithium fluoride, magnetically stirring at 35 ℃ for reaction for 24h, washing the reaction product until the supernatant is nearly neutral, and obtaining the multilayer two-dimensional transition metal carbide Nb2CTxThe obtained multilayer two-dimensional transition metal carbide Nb2CTxDispersing in deionized water, ultrasonically stripping, and centrifuging at 6000rpm for 10min to obtain two-dimensional transition metal carbide Nb2CTxA stable suspension of nanoplatelets;
2) adjusting two-dimensional transition metal carbide Nb2CTxThe concentration of the suspension is 20mg/mL, a cross-linking agent diethylenetriamine (40mg) is added into 10mL of the suspension obtained in the step 1), the suspension is guided to assemble to form hydrogel, the obtained hydrogel material is pre-frozen at the liquid nitrogen temperature of-196 ℃ for 0.5h, and then is subjected to vacuum freeze drying for 48h under the conditions that the temperature is 25 ℃ and the pressure is 10Pa to obtain Nb2CTxAn aerogel material;
3) the obtained Nb2CTxAerogel (200 mg) was immersed directly in 25mL of zinc nitrate (0.5M) in methanol and stirred at room temperature for 1h to promote zinc ion in Nb2CTxAdsorption of aerogel, addition of 25mL of 2-methylimidazole (0.5M) in methanol, reaction of the mixture at room temperature for 24 hoursWashing, vacuum filtering, pre-freezing at-196 deg.C liquid nitrogen for 0.5 hr, and vacuum freeze-drying at 25 deg.C under 10Pa for 48 hr to obtain Nb2CTxA ZIF-8 aerogel material.
Nb for example 22CTxThe ZIF-8 composite aerogel carries out related experiments, and the results are as follows:
FIG. 3 shows Nb prepared in example 22CTxScanning electron micrograph of/ZIF-8 composite aerogel, as can be seen from FIG. 3, Nb2CTxthe/ZIF-8 composite aerogel has a rich porous structure.
FIG. 4 shows Nb prepared in example 22CTxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions can be seen from figure 4, and the prepared Nb is2CTxthe/ZIF-8 composite aerogel can adsorb mercury ions to about 160mg/g, and shows better adsorption performance.
Example 3
The main differences between this embodiment and the specific embodiment 1 are: the prepared metal organic framework material is ZIF-67, and the specific steps are as follows:
1) 1.6g of lamellar MAX phase Ti3AlC2Adding ceramic powder into 20mL (9.0M) hydrochloric acid solution dissolved with 2.0g of lithium fluoride, magnetically stirring at 35 ℃ for reaction for 24h, washing the reaction product until the supernatant is nearly neutral, and obtaining multilayer two-dimensional transition metal carbide Ti3C2TxThe obtained multilayer two-dimensional transition metal carbide Ti3C2TxDispersing in deionized water, ultrasonically stripping, and centrifuging at 6000rpm for 10min to obtain two-dimensional transition metal carbide Ti3C2TxA stable suspension of nanoplatelets;
2) adjusting two-dimensional transition metal carbide Ti3C2TxThe concentration of the suspension is 20mg/mL, a cross-linking agent diethylenetriamine (40mg) is added into 10mL of the suspension obtained in the step 1) to guide the suspension to be assembled into hydrogel, and the obtained hydrogel material is pre-frozen at the liquid nitrogen temperature of-196 ℃ for 0.5h and then at the temperature of 25℃,Vacuum freeze-drying for 48h under the pressure of 10Pa to obtain Ti3C2TxAn aerogel material;
3) the obtained Ti3C2TxAerogel (200 mg) was directly soaked in 25mL of cobalt nitrate (0.5M) in methanol and stirred at room temperature for 1h to promote the formation of cobalt ions in the Ti3C2TxAdsorbing aerogel, adding 25mL of 2-methylimidazole (0.5M) methanol solution, reacting the mixture at room temperature for 24 hr, washing, vacuum filtering, pre-freezing at-196 deg.C liquid nitrogen temperature for 0.5 hr, and vacuum freeze-drying at 25 deg.C and 10Pa for 48 hr to obtain Ti3C2Tx/ZIF-67 aerogel materials.
Ti obtained in example 33C2TxThe ZIF-67 composite aerogel carries out related experiments, and the results are as follows:
FIG. 5 shows Ti prepared in example 33C2TxScanning electron micrograph of/ZIF-67 composite aerogel, as can be seen in FIG. 5, Ti3C2Txthe/ZIF-67 composite aerogel has a rich porous structure.
FIG. 6 is Ti prepared in example 33C2TxThe nitrogen adsorption and desorption isotherm of the/ZIF-67 composite aerogel can be calculated from the nitrogen adsorption isotherm in FIG. 6, and the prepared Ti3C2TxThe specific surface area of the/ZIF-67 composite aerogel is 480 m2 g-1。
Meanwhile, Ti prepared in example 33C2TxThe adsorption performance of the/ZIF-67 composite aerogel on heavy metal ions is tested, and the test shows that Ti is3C2Txthe/ZIF-67 composite aerogel can adsorb about 170mg/g of mercury ions and shows better adsorption performance.
Example 4
The main differences between this embodiment and the specific embodiment 1 are: the cross-linking agent is triethylene tetramine.
1) 1.6g of lamellar MAX phase Ti3AlC2Adding ceramic powder into 20mL hydrochloric acid (9.0M) solution dissolved with 2.0g of lithium fluoride, magnetically stirring at 35 ℃ for reaction for 24h, washing the reaction product until the supernatant is nearly neutral, and obtaining multilayer two-dimensional transition metal carbide Ti3C2TxThe obtained multilayer two-dimensional transition metal carbide Ti3C2TxDispersing in deionized water, ultrasonically stripping, and centrifuging at 6000rpm for 10min to obtain two-dimensional transition metal carbide Ti3C2TxA stable suspension of nanoplatelets;
2) adjusting two-dimensional transition metal carbide Ti3C2TxThe concentration of the suspension is 20mg/mL, a cross-linking agent triethylene tetramine (40mg) is added into 10mL of the suspension obtained in the step 1), the suspension is guided to be assembled to form hydrogel, the obtained hydrogel material is pre-frozen at the liquid nitrogen temperature of-196 ℃ for 0.5h, and then is subjected to vacuum freeze drying for 48h under the conditions that the temperature is 25 ℃ and the pressure is 10Pa to obtain Ti3C2TxAn aerogel material;
3) the obtained Ti3C2TxAerogel (200 mg) was immersed directly in 25mL of zinc nitrate (0.5M) in methanol and stirred at room temperature for 1h to promote the formation of zinc ions in the Ti3C2TxAdsorbing aerogel, adding 25mL of 2-methylimidazole (0.5M) methanol solution, reacting the mixture at room temperature for 24 hr, washing, vacuum filtering, pre-freezing at-196 deg.C liquid nitrogen temperature for 0.5 hr, and vacuum freeze-drying at 25 deg.C and 10Pa for 48 hr to obtain Ti3C2TxA ZIF-8 aerogel material.
For Ti obtained in example 13C2TxThe ZIF-8 composite aerogel carries out related experiments, and the results are as follows:
FIG. 7 shows Ti prepared in example 43C2TxScanning electron micrograph of/ZIF-8 composite aerogel, as can be seen from FIG. 7, Ti3C2Txthe/ZIF-8 composite aerogel has a rich porous structure.
FIG. 8 is a drawing showingTi prepared in example 43C2TxThe adsorption performance of the/ZIF-8 composite aerogel on heavy metal ions can be seen from figure 8, and the prepared Ti3C2Txthe/ZIF-8 composite aerogel can adsorb mercury ions to about 140mg/g and shows good adsorption performance.
The two-dimensional transition metal carbide/metal organic framework composite aerogels prepared in examples 1 to 4 were used as heavy metal ion adsorption materials. When the heavy metal ion adsorbing material is prepared, a two-dimensional transition metal carbide and a metal organic framework are introduced, wherein the two-dimensional transition metal carbide and the metal organic framework are respectively a novel two-dimensional layered material and a porous material with a high specific surface area, and the two-dimensional transition metal carbide and the metal organic framework have the following advantages as the adsorbing material: the two-dimensional transition metal carbide can form a three-dimensional network structure, which is beneficial to the load of other materials with high specific surface area; the metal organic framework material has large specific surface area and high porosity, and can provide more adsorption sites, thereby improving the adsorption capacity to metal ions.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. The preparation method of the two-dimensional transition metal carbide/metal organic framework composite aerogel material is characterized by comprising the following steps of:
1) adding layered MAX phase ceramic powder into hydrochloric acid solution dissolved with lithium fluoride, and magnetically stirring for reaction, wherein MAX phase ceramic is Ti3AlC2、Ti2AlC、Nb2AlC、V2AlC and Cr2One or more AlC is/are mixed, and the mass ratio of MAX-phase ceramic powder to lithium fluoride is 0.5-2: washing the reaction product until the supernatant is nearly neutral to obtain multilayer two-dimensional transition metal carbide, and dispersing the obtained multilayer two-dimensional transition metal carbideCentrifuging after ultrasonic stripping in deionized water to obtain a stable suspension of two-dimensional transition metal carbide nanosheets;
2) adjusting the concentration of the two-dimensional transition metal carbide suspension to 10-50 mg/mL, adding a cross-linking agent into the suspension obtained in the step 1) to guide the suspension to be assembled to form hydrogel, wherein the cross-linking agent is one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the mass ratio of the two-dimensional transition metal carbide to the cross-linking agent is 0.2-5: 1, obtaining a two-dimensional transition metal carbide aerogel material through vacuum freeze drying;
3) directly soaking the two-dimensional transition metal carbide aerogel prepared in the step 2) in a precursor solution of a metal organic framework material, reacting at room temperature, washing, and freeze-drying to obtain the two-dimensional transition metal carbide/metal organic framework composite aerogel material, wherein the mass ratio of the two-dimensional transition metal carbide to the metal organic framework material is 0.5-2: 1.
2. the preparation method of claim 1, wherein the temperature of the magnetic stirring in the step 1) is 30-50 ℃, and the time of the magnetic stirring is 6-48 h; the centrifugal rotating speed in the step 1) is 2000-6000 rpm, and the centrifugal time is 5-10 min.
3. The preparation method of claim 1, wherein the vacuum freeze-drying in step 2) is pre-freezing at-20 ℃ to-196 ℃ for 0.5 to 6 hours, and then freeze-drying at-45 ℃ to 40 ℃ under 2-50Pa for 6 to 48 hours.
4. The preparation method according to claim 1, wherein the precursor solution of the metal organic framework material in step 3) comprises a methanol solution of zinc nitrate and 2-methylimidazole for preparing ZIF-8, a methanol solution of cobalt nitrate and 2-methylimidazole for preparing ZIF-67; the reaction time is 2-48 h; the freeze drying refers to pre-freezing for 0.5-6 h at the temperature of-20 ℃ to-196 ℃, and freeze drying for 6-48 h at the temperature of-45 ℃ to 40 ℃ and under the pressure of 2-50 Pa.
5. The method according to claim 4, wherein the concentration of zinc nitrate in the precursor solution of the metal organic framework material is 0.1-1.0M, the concentration of cobalt nitrate is 0.1-1.0M, and the concentration of 2-methylimidazole is 0.1-1.0M.
6. A two-dimensional transition metal carbide/metal organic framework composite aerogel material is prepared by taking a three-dimensional network structure formed by two-dimensional transition metal carbide sheet layers as a substrate, loading a metal organic framework material on the two-dimensional transition metal carbide sheet layers,
the two-dimensional transition metal carbide is Ti3C2Tx、Ti2CTx、Nb2CTx、V2CTxAnd Cr2CTxOne or more of, TxIs one or the combination of-OH and-F,
the density of the composite aerogel is 0.06-0.8 g cm-3The specific surface area is 200-1500 m2 g-1。
7. Use of the two-dimensional transition metal carbide/metal organic framework composite aerogel material of claim 6 to adsorb metal ions.
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