WO2022165989A1 - Mxene material having organic chelating functional groups grafted on surface and preparation method therefor - Google Patents
Mxene material having organic chelating functional groups grafted on surface and preparation method therefor Download PDFInfo
- Publication number
- WO2022165989A1 WO2022165989A1 PCT/CN2021/087131 CN2021087131W WO2022165989A1 WO 2022165989 A1 WO2022165989 A1 WO 2022165989A1 CN 2021087131 W CN2021087131 W CN 2021087131W WO 2022165989 A1 WO2022165989 A1 WO 2022165989A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mxene
- mxene material
- suspension
- chelating functional
- functional groups
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 61
- 125000000524 functional group Chemical group 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- -1 aminoethylamino Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- JUESRADRPFMUCL-UHFFFAOYSA-N dimethoxy-methyl-(2-methylpropyl)silane Chemical compound CO[Si](C)(OC)CC(C)C JUESRADRPFMUCL-UHFFFAOYSA-N 0.000 claims description 2
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 claims description 2
- FPFKERZHIGFTEI-UHFFFAOYSA-N n'-(2-trimethoxysilylethyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCNCCN FPFKERZHIGFTEI-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 12
- 230000002285 radioactive effect Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000002242 deionisation method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 35
- 150000002500 ions Chemical class 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RXQXPMOQOKMLRT-UHFFFAOYSA-N n'-[[methoxy-methyl-(2-methylpropyl)silyl]oxymethyl]ethane-1,2-diamine Chemical compound CC(C)C[Si](C)(OC)OCNCCN RXQXPMOQOKMLRT-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/006—Radioactive compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Definitions
- the invention belongs to the field of Mxene material modification, in particular to an Mxene material with surface grafted organic chelating functional groups and a preparation method thereof.
- Capacitive deionization is a new water treatment technology that is efficient, environmentally friendly, easy to operate and economical. At present, it has been widely used in desalination and water softening. Based on the previous research results, CDI can also receive good results in the treatment of heavy metals and radioactive ions. However, heavy metals and radioactive ions are different from the light sodium, calcium, magnesium and other ions in desalination and softening. It is necessary to design and prepare the key core component of CDI, the electrode, and the key of the electrode is the active electrode material. Therefore, the key to this technology is to design electrode materials for the treatment of heavy metals and radioactive ions.
- Mxene As a new type of two-dimensional material, Mxene has received extensive research and attention since its inception in 2011. Due to its unique layered and crystalline structure, Mxene can be used as an excellent electrode material for CDI. However, for the adsorption and treatment of heavy metals and radioactive ions, it is difficult to achieve efficient and thorough removal by pure Mxene alone, and the anchoring of these ions by pure Mxene is not stable. Although there are reports on the introduction of active hydroxyl groups on the surface of Mxene to remove lead ions, the adsorption capacity of this material is limited, and the material cannot be regenerated and cannot be reused.
- the purpose of the present invention is to provide an Mxene material with surface grafted organic chelating functional groups, which has good conductivity, high adsorption capacity, fast efficiency, and can be regenerated and reused.
- Another object of the present invention is to provide a preparation method of Mxene material with simple process flow, simple and convenient operation, and industrialized production.
- An Mxene material with an organic chelating functional group grafted on the surface is characterized in that, the Mxene material and a grafting agent are combined through a silicon-oxygen bond, and the grafting agent contains an amino group and/or a carboxyl group as the organic chelating functional group.
- the surface of the Mxene material of the present invention is grafted with a large number of organic chelating functional groups (amino groups, carboxyl groups) through covalent bonds, and these chelating functional groups can strongly anchor the heavy metal ions in the polluted water body (such as Lead, mercury, cadmium, strontium) and radioactive ions (such as cesium), the adsorption capacity can reach 210 mg g -1 , the removal efficiency can reach 99%, and the adsorption rate is extremely fast (close to equilibrium in 5 minutes).
- organic chelating functional groups amino groups, carboxyl groups
- these chelating functional groups can strongly anchor the heavy metal ions in the polluted water body (such as Lead, mercury, cadmium, strontium) and radioactive ions (such as cesium)
- the adsorption capacity can reach 210 mg g -1
- the removal efficiency can reach 99%
- the adsorption rate is extremely fast (close to equilibrium in 5 minutes).
- Mxene without chelating functional group modification has only half the adsorption capacity of the Mxene material of the present invention, and the removal efficiency is less than 90%.
- the Mxene material used in the invention has numerous and uniform hydroxyl functional groups on the surface during the etching preparation process, which can provide adsorption active sites for the grafting and chelating functional groups, and one end of the grafting agent has a silane functional group, which can be hydrolyzed.
- the polymerization reaction occurs with the hydroxyl group on the surface of Mxene to form a stable silicon-oxygen bond, thereby realizing the grafting of chelating functional groups to the surface of Mxene.
- the Mxene material of the present invention can realize complete removal and regeneration in an external reverse electric field, thereby realizing efficient recycling.
- An external reverse electric field can give a strong driving force to the metal ions, so that the chelated bonds are broken after activation, thereby realizing the regeneration of the material.
- the regeneration process does not require acid washing, so there is no secondary pollution. However, there is no such regeneration ability after the use of Mxene materials to adsorb heavy metals.
- the preparation process of the invention is controllable and simple, the operation is simple, the material morphology and structure are good, the number of chelating functional groups grafted on the surface is considerable and uniform, and as a capacitive deionization electrode material, the performance of removing heavy metal ions and radioactive ions is excellent, thereby realizing water. Efficient treatment, and materials can be recycled and reused, and it has large-scale industrial production and application prospects.
- Fig. 1 is the SEM image of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
- Fig. 2 is the XRD pattern of the Mxene material of embodiment 1 surface grafting organic chelating functional group
- Fig. 3 is the FTIR image of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
- Fig. 4 is the adsorption isotherm of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
- FIG. 5 is the regeneration mechanism curve of the Mxene material grafted with organic chelating functional groups on the surface of Example 1.
- the Mxene material according to claim 1 or 2 wherein the grafting agent is selected from N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid, N-(3-trimethoxysilylpropyl) ethylenediamine, N-(3-trimethoxysilylethyl)ethylenediamine, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, aminoethylamino At least one of isobutylmethyldimethoxysilane.
- the solid content of described suspension I is 1 ⁇ 10 g/L
- the concentration of the grafting agent in the solution II is 2-10 wt%.
- Figure 1 is the SEM image of the Mxene material. It can be seen that Mxene is in the shape of a louver formed by stacking two-dimensional nanosheets;
- Figure 2 is the XRD pattern of the Mxene material, which shows that the Mxene crystallizes well, and there is basically no other impurity phase;
- Figure 3 is the FTIR image of the Mxene material.
- the stretching vibration peak of the hydroxyl group appears at 3400 cm -1 , which proves that the EDTA chain (its organic chelating functional group is a carboxyl group) has been successfully grafted to the surface of Mxene;
- 200mg of Mxene material is made into an electrode, which is used for CDI adsorption concentration of 50ppm and 200mL of solution containing heavy metal ions or radioactive ions (such as lead, mercury, cadmium, strontium, cesium, etc.) Divide by the initial concentration to obtain the removal efficiency.
- the adsorption capacity test can refer to existing literature methods (such as Environ. Sci.: Nano, 2017, 4, 1114–1123), and the adsorption time was 5 min.
- Figure 4 is the cesium ion adsorption isotherm of the Mxene material. It can be seen that the adsorption capacity of the material is 210 mg g -1 and the removal efficiency is 99.6%.
- Mxene without chelating functional group modification has an adsorption capacity of 99.8 mg g -1 and a removal efficiency of 86.4%.
- Figure 5 is the regeneration mechanism curve of the Mxene material.
- the material was slowly applied from 0V to 1.6V, and then the voltage was slowly reduced to -1.4V, and the concentration of the solution was monitored in real time and the adsorption capacity was calculated.
- This experiment shows that almost all the adsorbed cesium ions can be reversibly removed at a voltage of -1.4V, the process only needs to apply a reverse electric field, no acid elution and adsorption, no secondary pollution, and it is convenient and fast.
- the Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
- the effective chelating functional group grafted on the surface of the Mxene material in this embodiment is an amino group, which can effectively chelate and remove heavy metal ions as a CDI electrode material.
- the adsorption experiment was carried out with reference to the method of Example 1, the lead adsorption capacity was 310.3 mg g -1 , and the removal efficiency was 99.5%.
- Mxene without chelating functional group modification has an adsorption capacity of 152.3 mg g -1 and a removal efficiency of 83.9%.
- the Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
- the Mxene material of this example has excellent chelation and removal efficiency for heavy metal ions, and the material is regenerable.
- the adsorption experiment was carried out with reference to the method of Example 1.
- the adsorption capacity of copper ions was 75.6 mg g -1 , and the removal efficiency was 99.0%.
- Mxene without chelating functional group modification has an adsorption capacity of 32.1 mg g -1 and a removal efficiency of 88.3%.
- the Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
- suspension I solid content is 1 g/L
- grafting agent N-(2-aminoethyl) -3-Aminopropylmethyldiethoxysilane was added to 1.2 mL of methanol to obtain solution II (9.54 wt%), which was mixed uniformly for later use;
- the adsorption experiment was carried out with reference to the method of Example 1.
- the adsorption capacity of copper was 85.2 mg g ⁇ 1 , and the removal efficiency was 99.4%.
- Mxene without chelating functional group modification has an adsorption capacity of 35.1 mg g -1 and a removal efficiency of 89.3%.
- the Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
- the adsorption experiment was carried out with reference to the method of Example 1, the lead adsorption capacity was 325 mg g -1 , and the removal efficiency was 99.4%.
- Mxene without chelating functional group modification has a lead adsorption capacity of 152 mg g -1 and a removal efficiency of 88.5%.
- the Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
- the adsorption experiment was carried out with reference to the method of Example 1.
- the adsorption capacity of cesium was 196.3 mg g ⁇ 1 , and the removal efficiency was 99.5%.
- Mxene without chelating functional group modification has a cesium adsorption capacity of 85.8 mg g -1 and a removal efficiency of 85.8%.
- the present application has industrial applicability.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to the field of Mxene material modification. Disclosed is an Mxene material having organic chelating functional groups grafted on the surface. The Mxene material is combined with a grafting agent by means of a silicon-oxygen bond, and the grafting agent contains amino and/or carboxyl as the organic chelating functional groups. Also disclosed in the present invention is a preparation method for a Mxene material, comprising: S1, dispersing Mxene powder in an organic solvent to obtain a suspension I, and adding a grafting agent into the organic solvent to obtain a solution II; and S2, adding the solution II into the suspension I, carrying out stirring reaction under an ultrasonic condition, then separating a solid, and cleaning and drying to obtain a product. The preparation process of the present invention is controllable and simple, and easy and convenient to operate; the material is good in morphology and structure, has a considerable number of uniform organic chelating functional groups grafted on the surface, and as a capacitive deionization electrode material, has excellent heavy metal ion and radioactive ion removal performance, so as to achieve efficient treatment of water; and the material can be regenerated and recycled, and has large-scale industrial production and application prospects.
Description
本发明属于Mxene材料改性领域，具体是一种表面接枝有机螯合官能团的Mxene材料及其制备方法。The invention belongs to the field of Mxene material modification, in particular to an Mxene material with surface grafted organic chelating functional groups and a preparation method thereof.
自从人类踏入工业社会与开发应用核能源以来，重金属与放射性离子的污染一直是严重威胁人类健康与生态环境的环境问题。如何高效治理这些工业污染一直是研究学者们的课题重心。尽管目前开发了许多传统的办法来治理重金属与放射性离子的污染，但都面临一些实际应用问题，如效率不高，对低浓度离子效果不佳，处理物造成二次污染，无法再生造成成本高昂等等。因此开发新型治理策略尤为迫切。Since humans entered the industrial society and developed and applied nuclear energy, the pollution of heavy metals and radioactive ions has always been an environmental problem that seriously threatens human health and the ecological environment. How to effectively control these industrial pollution has always been the focus of research scholars. Although many traditional methods have been developed to control the pollution of heavy metals and radioactive ions, they all face some practical application problems, such as low efficiency, poor effect on low-concentration ions, secondary pollution of treated materials, and high cost due to inability to regenerate. and many more. Therefore, it is particularly urgent to develop new governance strategies.
电容去离子化（capacitive deionization，CDI）是一种高效、环保、操作简便和经济的新型水处理技术。目前已大规模应用在除盐和水体软化上。基于前面的这些研究成果，CDI对重金属与放射性离子的治理也可以收到良好的效果。然而，重金属与放射性离子不同于除盐和软化中的轻型钠、钙、镁等离子，需要相应地针对性设计与制备CDI的关键核心部件——电极，而电极的关键就是其中的活性电极材料。因此，该技术的关键就是设计针对治理重金属与放射性离子的电极材料。Capacitive deionization (CDI) is a new water treatment technology that is efficient, environmentally friendly, easy to operate and economical. At present, it has been widely used in desalination and water softening. Based on the previous research results, CDI can also receive good results in the treatment of heavy metals and radioactive ions. However, heavy metals and radioactive ions are different from the light sodium, calcium, magnesium and other ions in desalination and softening. It is necessary to design and prepare the key core component of CDI, the electrode, and the key of the electrode is the active electrode material. Therefore, the key to this technology is to design electrode materials for the treatment of heavy metals and radioactive ions.
Mxene作为一种新型二维材料自2011年问世以来就受到了广泛的研究与关注。由于其独特的层状结构与晶体结构，Mxene可以作为一种优秀电极材料应用于CDI。然而针对重金属与放射性离子的吸附与治理，光靠纯的Mxene难以实现高效、彻底的去除，且纯Mxene对这些离子的锚固并不稳定。虽然目前有在Mxene表面引入活性羟基用于去除铅离子的报导，但是该材料吸附容量有限，且材料不可再生从，不能重复利用。也有在Ti
3C
2T
x
Mexne上负载纳米银颗粒用于除盐的报导，但是银是贵金属，成本高昂，不利于大规模应用。因此研究开发一种表面官能团改性的、廉价高效的Mxene应用于重金属与放射性离子治理尤为迫切。
As a new type of two-dimensional material, Mxene has received extensive research and attention since its inception in 2011. Due to its unique layered and crystalline structure, Mxene can be used as an excellent electrode material for CDI. However, for the adsorption and treatment of heavy metals and radioactive ions, it is difficult to achieve efficient and thorough removal by pure Mxene alone, and the anchoring of these ions by pure Mxene is not stable. Although there are reports on the introduction of active hydroxyl groups on the surface of Mxene to remove lead ions, the adsorption capacity of this material is limited, and the material cannot be regenerated and cannot be reused. There are also reports of nano-silver particles supported on Ti 3 C 2 T x Mexne for desalination, but silver is a precious metal, and the cost is high, which is not conducive to large-scale applications. Therefore, it is particularly urgent to develop a cheap and efficient Mxene modified with surface functional groups for the treatment of heavy metals and radioactive ions.
本发明的目的是提供一种导电性好、吸附容量高、效率快、可再生重复使用的表面接枝有机螯合官能团的Mxene材料。The purpose of the present invention is to provide an Mxene material with surface grafted organic chelating functional groups, which has good conductivity, high adsorption capacity, fast efficiency, and can be regenerated and reused.
本发明的另一目的是提供一种工艺流程简单、操作简便、可实现产业化生产的Mxene材料的制备方法。Another object of the present invention is to provide a preparation method of Mxene material with simple process flow, simple and convenient operation, and industrialized production.
一种表面接枝有机螯合官能团的Mxene材料，其特征在于，所述Mxene材料与枝接剂通过硅氧键结合，枝接剂含有氨基和/或羧基作为有机螯合官能团。An Mxene material with an organic chelating functional group grafted on the surface is characterized in that, the Mxene material and a grafting agent are combined through a silicon-oxygen bond, and the grafting agent contains an amino group and/or a carboxyl group as the organic chelating functional group.
一种权利要求1~4任意一项所述的Mxene材料的制备方法，其特征在于，包括以下步骤：A preparation method of the Mxene material according to any one of claims 1 to 4, characterized in that, comprising the following steps:
S1、将Mxene粉末分散于有机溶剂中得到悬浮液Ⅰ，再将接枝剂加入有机溶剂中得到溶液Ⅱ；S1. Disperse the Mxene powder in an organic solvent to obtain suspension I, and then add the grafting agent into the organic solvent to obtain solution II;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，在超声条件下搅拌反应，然后分离出固体，经清洗、干燥得到产物。S2. The solution II is added to the suspension I, and the reaction is stirred under ultrasonic conditions, and then the solid is separated, washed and dried to obtain the product.
本发明具有以下有益效果：本发明的Mxene材料表面通过共价键接枝有大量的有机鳌合官能团（氨基、羧基），这些鳌合官能团能强力地锚固住被污染水体中的重金属离子（例如铅、汞、镉、锶）与放射性离子（如铯），吸附容量可达210
mg g
-1，去除效率可达99%，且吸附速率极快（5min接近平衡）。这是因为接枝在Mxene表面的螯合官能团具有强力的对重金属离子的捕获能力，可以在其表面充当吸附活性位点，提升Mxene的表面吸附活性，从而提升其吸附容量、去除效率以及加速吸附动力学。相比之下，没有螯合官能团改性的Mxene，吸附容量只有本发明Mxene材料的一半，且去除效率不到90%。
The present invention has the following beneficial effects: the surface of the Mxene material of the present invention is grafted with a large number of organic chelating functional groups (amino groups, carboxyl groups) through covalent bonds, and these chelating functional groups can strongly anchor the heavy metal ions in the polluted water body (such as Lead, mercury, cadmium, strontium) and radioactive ions (such as cesium), the adsorption capacity can reach 210 mg g -1 , the removal efficiency can reach 99%, and the adsorption rate is extremely fast (close to equilibrium in 5 minutes). This is because the chelating functional groups grafted on the surface of Mxene have a strong ability to capture heavy metal ions, and can act as adsorption active sites on the surface to enhance the surface adsorption activity of Mxene, thereby improving its adsorption capacity, removal efficiency and accelerated adsorption. dynamics. In contrast, Mxene without chelating functional group modification has only half the adsorption capacity of the Mxene material of the present invention, and the removal efficiency is less than 90%.
本发明采用的Mxene材料在刻蚀制备过程中表面带有众多且均匀的羟基官能团，可以为接枝鳌合官能团提供吸附活性位点，接枝剂的一端具有硅烷官能团，该官能团可以在水解后与Mxene表面的羟基发生聚合反应，形稳定的硅氧键，从而实现鳌合官能团接枝到Mxene表面。The Mxene material used in the invention has numerous and uniform hydroxyl functional groups on the surface during the etching preparation process, which can provide adsorption active sites for the grafting and chelating functional groups, and one end of the grafting agent has a silane functional group, which can be hydrolyzed. The polymerization reaction occurs with the hydroxyl group on the surface of Mxene to form a stable silicon-oxygen bond, thereby realizing the grafting of chelating functional groups to the surface of Mxene.
本发明的Mxene材料可以在外加反向电场中实现完全脱除再生，从而实现高效循环使用。外加反向电场可以给金属离子强力的驱动力，使其活化后鳌合键断裂，从而实现材料的再生。该再生过程不需要酸洗，因此无二次污染产生。而利用Mxene材料吸附重金属之后则没有这样的再生能力。The Mxene material of the present invention can realize complete removal and regeneration in an external reverse electric field, thereby realizing efficient recycling. An external reverse electric field can give a strong driving force to the metal ions, so that the chelated bonds are broken after activation, thereby realizing the regeneration of the material. The regeneration process does not require acid washing, so there is no secondary pollution. However, there is no such regeneration ability after the use of Mxene materials to adsorb heavy metals.
本发明制备工艺可控简单、操作简便，材料形貌结构良好，表面所接枝的鳌合官能团数量可观且均匀，作为电容去离子化电极材料去除重金属离子与放射性离子性能优异，从而实现水的高效治理，且材料可再生循环利用，具有大规模产业化生产与应用前景。The preparation process of the invention is controllable and simple, the operation is simple, the material morphology and structure are good, the number of chelating functional groups grafted on the surface is considerable and uniform, and as a capacitive deionization electrode material, the performance of removing heavy metal ions and radioactive ions is excellent, thereby realizing water. Efficient treatment, and materials can be recycled and reused, and it has large-scale industrial production and application prospects.
图1是实施例1表面接枝有机螯合官能团的Mxene材料的SEM图；Fig. 1 is the SEM image of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
图2是实施例1表面接枝有机螯合官能团的Mxene材料的XRD图；Fig. 2 is the XRD pattern of the Mxene material of embodiment 1 surface grafting organic chelating functional group;
图3是实施例1表面接枝有机螯合官能团的Mxene材料的FTIR图；Fig. 3 is the FTIR image of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
图4是实施例1表面接枝有机螯合官能团的Mxene材料的吸附等温线；Fig. 4 is the adsorption isotherm of the Mxene material with organic chelating functional groups grafted on the surface of Example 1;
图5是实施例1表面接枝有机螯合官能团的Mxene材料的再生机制曲线。FIG. 5 is the regeneration mechanism curve of the Mxene material grafted with organic chelating functional groups on the surface of Example 1. FIG.
根据权利要求1所述的Mxene材料，其特征在于，所述Mxene材料为Ti
3C
2。
The Mxene material according to claim 1, wherein the Mxene material is Ti 3 C 2 .
根据权利要求2所述的Mxene材料，其特征在于，所述Mxene材料的目数为200 ~800目。The Mxene material according to claim 2, wherein the Mxene material has a mesh number of 200-800 mesh.
根据权利要求1或2所述的Mxene材料，其特征在于，所述枝接剂选自N-(三甲氧基硅丙基)乙二胺三乙酸、N-(3-三甲氧基硅基丙基)乙二胺、N-(3-三甲氧基硅基乙基)乙二胺、N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷、氨基乙基氨基异丁基甲基二甲氧基硅烷中的至少一种。The Mxene material according to claim 1 or 2, wherein the grafting agent is selected from N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid, N-(3-trimethoxysilylpropyl) ethylenediamine, N-(3-trimethoxysilylethyl)ethylenediamine, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, aminoethylamino At least one of isobutylmethyldimethoxysilane.
根据权利要求5所述的方法，其特征在于，所述悬浮液Ⅰ的固含量为1~10
g/L，所述溶液Ⅱ的接枝剂浓度为2~10wt%。method according to claim 5, is characterized in that, the solid content of described suspension I is 1～10
g/L, the concentration of the grafting agent in the solution II is 2-10 wt%.
根据权利要求5所述的方法，其特征在于，所述S2中悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.01~0.1。The method according to claim 5, wherein the volume ratio of the suspension I and the solution II in the S2 is 1:0.01-0.1.
根据权利要求5所述的方法，其特征在于，所述有机溶剂为乙醇或甲醇。The method according to claim 5, wherein the organic solvent is ethanol or methanol.
根据权利要求5所述的方法，其特征在于，所述清洗是依次用洗涤溶剂和水清洗，所述洗涤溶剂为甲醇、乙醇、乙二醇、丙酮、甲苯中的至少一种。The method according to claim 5, characterized in that, the cleaning is sequentially cleaning with a washing solvent and water, and the washing solvent is at least one of methanol, ethanol, ethylene glycol, acetone, and toluene.
根据权利要求5所述的方法，其特征在于，所述S2中反应的温度为50~80℃，反应的时间为5~15h。The method according to claim 5, wherein the temperature of the reaction in the S2 is 50-80°C, and the reaction time is 5-15h.
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below with reference to specific embodiments.
实施例1Example 1
按照以下步骤制备接枝有机螯合官能团的Mxene材料The following steps were followed to prepare Mxene materials grafted with organic chelating functional groups
S1、将1g、400目Ti
3C
2粉末超声并磁力搅拌分散于200mL乙醇中得到悬浮液Ⅰ（固含量为5 g/L），再将200
mg N-(三甲氧基硅丙基)乙二胺三乙酸加入10mL乙醇中得到溶液Ⅱ（2.47 wt%），混合均匀备用；
S1. Disperse 1 g, 400 mesh Ti 3 C 2 powder in 200 mL of ethanol by ultrasonic and magnetic stirring to obtain suspension I (solid content of 5 g/L), and then add 200 mg of N-(trimethoxysilylpropyl)ethyl Diamine triacetic acid was added to 10 mL of ethanol to obtain solution II (2.47 wt%), which was mixed uniformly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.05，超声并搅拌混合均匀，在65℃下搅拌反应12h，然后离心分离出黑色固体，用乙醇和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add solution II to suspension I. The volume ratio of suspension I and solution II is 1:0.05. Ultrasonic and stir to mix evenly. Stir and react at 65 °C for 12 h, and then centrifuge to separate the black solid. After cleaning, the final product was obtained by drying in a blast drying oven at 80 °C for 12 h.
图1是Mxene材料的SEM图，可以看出Mxene呈由二维纳米片堆叠而成的百叶窗形状；Figure 1 is the SEM image of the Mxene material. It can be seen that Mxene is in the shape of a louver formed by stacking two-dimensional nanosheets;
图2是Mxene材料的XRD图，显示Mxene的结晶良好，基本无其他杂相出现；Figure 2 is the XRD pattern of the Mxene material, which shows that the Mxene crystallizes well, and there is basically no other impurity phase;
图3是Mxene材料的FTIR图，在3400cm
-1出现羟基的伸缩振动峰，证明乙二胺三乙酸链（其有机鳌合官能团为羧基）已经成功接枝到Mxene表面；
Figure 3 is the FTIR image of the Mxene material. The stretching vibration peak of the hydroxyl group appears at 3400 cm -1 , which proves that the EDTA chain (its organic chelating functional group is a carboxyl group) has been successfully grafted to the surface of Mxene;
将200mg的Mxene材料制成电极，用于CDI吸附浓度为50ppm 200mL的含有重金属离子或放射性离子（如铅、汞、镉、锶、铯等）的溶液，持续1h后测试残留铜离子浓度，再除以初始浓度得出去除效率。吸附容量的测试可以参照现有文献的方法（比如Environ.
Sci.: Nano, 2017, 4, 1114–1123）进行，吸附时间为5min。200mg of Mxene material is made into an electrode, which is used for CDI adsorption concentration of 50ppm and 200mL of solution containing heavy metal ions or radioactive ions (such as lead, mercury, cadmium, strontium, cesium, etc.) Divide by the initial concentration to obtain the removal efficiency. The adsorption capacity test can refer to existing literature methods (such as Environ.
Sci.: Nano, 2017, 4, 1114–1123), and the adsorption time was 5 min.
图4是Mxene材料的铯离子吸附等温线，可以看出该材料的吸附铯离子的容量为210
mg g
-1，去除效率为99.6%。
Figure 4 is the cesium ion adsorption isotherm of the Mxene material. It can be seen that the adsorption capacity of the material is 210 mg g -1 and the removal efficiency is 99.6%.
对比实验：没有螯合官能团改性的Mxene，吸附容量为99.8 mg g
-1，去除效率为86.4%。
Comparative experiment: Mxene without chelating functional group modification has an adsorption capacity of 99.8 mg g -1 and a removal efficiency of 86.4%.
图5是Mxene材料的再生机制曲线，该实验是将材料慢慢从0V加电压至1.6V，再将电压慢慢减至-1.4V，并实时监测溶液浓度并计算出吸附容量。该实验表明，在-1.4V的电压下，几乎所有吸附的铯离子都可逆的脱除出来，过程只需加反向电场，无需酸洗脱附，无二次污染，方便快捷。Figure 5 is the regeneration mechanism curve of the Mxene material. In this experiment, the material was slowly applied from 0V to 1.6V, and then the voltage was slowly reduced to -1.4V, and the concentration of the solution was monitored in real time and the adsorption capacity was calculated. This experiment shows that almost all the adsorbed cesium ions can be reversibly removed at a voltage of -1.4V, the process only needs to apply a reverse electric field, no acid elution and adsorption, no secondary pollution, and it is convenient and fast.
实施例2Example 2
按照以下步骤制备接枝有机螯合官能团的Mxene材料：The Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
S1、将1g、400目Ti
3C
2粉末超声并磁力搅拌分散于200mL乙醇中得到悬浮液Ⅰ（固含量为5 g/L），再将300
mg N-(3-三甲氧基硅基乙基)乙二胺加入10mL乙醇中得到溶液Ⅱ（3.66 wt%），混合均匀备用；
S1. Disperse 1 g, 400 mesh Ti 3 C 2 powder in 200 mL of ethanol with ultrasonic and magnetic stirring to obtain suspension I (solid content is 5 g/L), and then add 300 mg of N-(3-trimethoxysilylethyl ether) base) ethylenediamine was added to 10 mL of ethanol to obtain solution II (3.66 wt%), which was mixed evenly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.05，超声并搅拌混合均匀，在65℃下搅拌反应12h，然后离心分离出黑色固体，用乙醇和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add solution II to suspension I. The volume ratio of suspension I and solution II is 1:0.05. Ultrasonic and stir to mix evenly. Stir and react at 65 °C for 12 h, and then centrifuge to separate the black solid. After cleaning, the final product was obtained by drying in a blast drying oven at 80 °C for 12 h.
本实施例的Mxene材料表面接枝的有效鳌合官能团为氨基，作为CDI电极材料可以有效鳌合去除重金属离子。参照实施例1的方法进行吸附实验，其吸附铅的容量为310.3 mg g
-1，去除效率为99.5%。
The effective chelating functional group grafted on the surface of the Mxene material in this embodiment is an amino group, which can effectively chelate and remove heavy metal ions as a CDI electrode material. The adsorption experiment was carried out with reference to the method of Example 1, the lead adsorption capacity was 310.3 mg g -1 , and the removal efficiency was 99.5%.
对比实验：没有螯合官能团改性的Mxene，吸附容量为152.3 mg g
-1，去除效率为83.9%。
Comparative experiment: Mxene without chelating functional group modification has an adsorption capacity of 152.3 mg g -1 and a removal efficiency of 83.9%.
实施例3Example 3
按照以下步骤制备接枝有机螯合官能团的Mxene材料：The Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
S1、将1g、800目Ti
3C
2粉末超声并磁力搅拌分散于200mL乙醇中得到悬浮液Ⅰ（固含量为5 g/L），再将400
mg N-(3-三甲氧基硅基丙基)乙二胺加入10mL乙醇中得到溶液Ⅱ（4.83 wt%），混合均匀备用；
S1. Disperse 1 g, 800 mesh Ti 3 C 2 powder in 200 mL of ethanol with ultrasonic and magnetic stirring to obtain suspension I (solid content is 5 g/L), and then add 400 mg of N-(3-trimethoxysilylpropane) base) ethylenediamine was added to 10 mL of ethanol to obtain solution II (4.83 wt%), which was mixed evenly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.05，超声并搅拌混合均匀，在75℃下搅拌反应10h，然后离心分离出黑色固体，用甲醇和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add solution II to suspension I. The volume ratio of suspension I and solution II is 1:0.05. Ultrasonic and stir to mix evenly. Stir and react at 75 °C for 10 h, and then centrifuge to separate the black solid. After cleaning, the final product was obtained by drying in a blast drying oven at 80 °C for 12 h.
本实施例的Mxene材料对重金属离子的鳌合去除效率优良，且材料可再生，参照实施例1的方法进行吸附实验，其吸附铜离子的容量为75.6mg g
-1，去除效率为99.0%。
The Mxene material of this example has excellent chelation and removal efficiency for heavy metal ions, and the material is regenerable. The adsorption experiment was carried out with reference to the method of Example 1. The adsorption capacity of copper ions was 75.6 mg g -1 , and the removal efficiency was 99.0%.
对比实验：没有螯合官能团改性的Mxene，吸附容量为32.1mg g
-1，去除效率为88.3%。
Comparative experiment: Mxene without chelating functional group modification has an adsorption capacity of 32.1 mg g -1 and a removal efficiency of 88.3%.
实施例4Example 4
按照以下步骤制备接枝有机螯合官能团的Mxene材料：The Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
S1、将3g、200目Ti
3C
2粉末超声并磁力搅拌分散于3000mL甲醇中得到悬浮液Ⅰ（固含量为1g/L），再将100 mg接枝剂N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷加入1.2mL甲醇中得到溶液Ⅱ（9.54wt%），混合均匀备用；
S1. Disperse 3g, 200 mesh Ti 3 C 2 powder in 3000 mL methanol with ultrasonic and magnetic stirring to obtain suspension I (solid content is 1 g/L), and then add 100 mg of grafting agent N-(2-aminoethyl) -3-Aminopropylmethyldiethoxysilane was added to 1.2 mL of methanol to obtain solution II (9.54 wt%), which was mixed uniformly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.1，超声并搅拌混合均匀，在55℃下搅拌反应15h，然后离心分离出黑色固体，用丙酮和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add the solution II to the suspension I, the volume ratio of the suspension I and the solution II is 1:0.1, ultrasonically and stir to mix evenly, stir and react at 55 ° C for 15 hours, and then centrifuge to separate the black solid, and use acetone and water After cleaning, the final product was obtained by drying in a blast drying oven at 80 °C for 12 h.
参照实施例1的方法进行吸附实验，其吸附铜的容量为85.2
mg g
-1，去除效率为99.4%。
The adsorption experiment was carried out with reference to the method of Example 1. The adsorption capacity of copper was 85.2 mg g −1 , and the removal efficiency was 99.4%.
对比实验：没有螯合官能团改性的Mxene，吸附容量为35.1 mg g
-1，去除效率为89.3%。
Comparative experiment: Mxene without chelating functional group modification has an adsorption capacity of 35.1 mg g -1 and a removal efficiency of 89.3%.
实施例5Example 5
按照以下步骤制备接枝有机螯合官能团的Mxene材料：The Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
S1、将5g、600目Ti
3C
2粉末超声并磁力搅拌分散于500mL乙醇中得到悬浮液Ⅰ（固含量为10 g/L），再将500
mg接枝剂氨基乙基氨基异丁基甲基二甲氧基硅烷加入10mL乙醇中得到溶液Ⅱ（5.96wt%），混合均匀备用；
S1. Disperse 5g, 600 mesh Ti 3 C 2 powder in 500 mL of ethanol by ultrasonic and magnetic stirring to obtain suspension I (solid content is 10 g/L), and then add 500 mg of the grafting agent aminoethylaminoisobutylmethyldi Methoxysilane was added to 10 mL of ethanol to obtain solution II (5.96 wt%), which was mixed evenly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.01，超声并搅拌混合均匀，在80℃下搅拌反应8h，然后离心分离出黑色固体，用乙二醇和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add solution II to suspension I, the volume ratio of suspension I and solution II is 1:0.01, ultrasonically and stir to mix evenly, stir and react at 80°C for 8 hours, and then centrifuge to separate the black solid, and use ethylene glycol and After washing with water, it was dried in a blast drying oven at 80 °C for 12 h to obtain the final product.
参照实施例1的方法进行吸附实验，其吸附铅的容量为325
mg g
-1，去除效率为99.4%。
The adsorption experiment was carried out with reference to the method of Example 1, the lead adsorption capacity was 325 mg g -1 , and the removal efficiency was 99.4%.
对比实验：没有螯合官能团改性的Mxene，吸附铅容量为152 mg g
-1，去除效率为88.5%。
Comparative experiment: Mxene without chelating functional group modification has a lead adsorption capacity of 152 mg g -1 and a removal efficiency of 88.5%.
实施例6Example 6
按照以下步骤制备接枝有机螯合官能团的Mxene材料：The Mxene materials grafted with organic chelating functional groups were prepared according to the following steps:
S1、将4g、400目Ti
3C
2粉末超声并磁力搅拌分散于500mL乙醇中得到悬浮液Ⅰ（固含量为8g/L），再将250 mg接枝剂N-(3-三甲氧基硅基丙基)乙二胺加入3.5mL乙醇中得到溶液Ⅱ（8.30wt%），混合均匀备用；
S1. Disperse 4g, 400 mesh Ti 3 C 2 powder in 500 mL of ethanol by ultrasonic and magnetic stirring to obtain suspension I (solid content is 8 g/L), and then add 250 mg of grafting agent N-(3-trimethoxysilicon) propyl) ethylenediamine was added to 3.5 mL of ethanol to obtain solution II (8.30 wt%), which was mixed evenly for later use;
S2、将溶液Ⅱ加入悬浮液Ⅰ中，悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.03，超声并搅拌混合均匀，在50℃下搅拌反应5h，然后离心分离出黑色固体，用甲苯和水清洗后，在80℃的鼓风干燥箱中干燥12h得到最终产物。S2. Add solution II to suspension I. The volume ratio of suspension I and solution II is 1:0.03. Ultrasonic and stir to mix evenly. Stir and react at 50 °C for 5 h, and then centrifuge to separate the black solid. After cleaning, the final product was obtained by drying in a blast drying oven at 80 °C for 12 h.
参照实施例1的方法进行吸附实验，其吸附铯的容量为196.3
mg g
-1，去除效率为99.5%。
The adsorption experiment was carried out with reference to the method of Example 1. The adsorption capacity of cesium was 196.3 mg g −1 , and the removal efficiency was 99.5%.
对比实验：没有螯合官能团改性的Mxene，吸附铯容量为85.8mg g
-1，去除效率为85.8%。
Comparative experiment: Mxene without chelating functional group modification has a cesium adsorption capacity of 85.8 mg g -1 and a removal efficiency of 85.8%.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, All should be included within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
本申请具有工业实用性。The present application has industrial applicability.
Claims (10)
- 一种表面接枝有机螯合官能团的Mxene材料，其特征在于，所述Mxene材料与枝接剂通过硅氧键结合，枝接剂含有氨基和/或羧基作为有机螯合官能团。An Mxene material with an organic chelating functional group grafted on the surface is characterized in that, the Mxene material and a grafting agent are combined through a silicon-oxygen bond, and the grafting agent contains an amino group and/or a carboxyl group as the organic chelating functional group.
- 根据权利要求1所述的Mxene材料，其特征在于，所述Mxene材料为Ti 3C 2。 The Mxene material according to claim 1, wherein the Mxene material is Ti 3 C 2 .
- 根据权利要求2所述的Mxene材料，其特征在于，所述Mxene材料的目数为200 ~800目。The Mxene material according to claim 2, wherein the Mxene material has a mesh number of 200-800 mesh.
- 根据权利要求1或2所述的Mxene材料，其特征在于，所述枝接剂选自N-(三甲氧基硅丙基)乙二胺三乙酸、N-(3-三甲氧基硅基丙基)乙二胺、N-(3-三甲氧基硅基乙基)乙二胺、N-(2-氨乙基)-3-氨丙基甲基二乙氧基硅烷、氨基乙基氨基异丁基甲基二甲氧基硅烷中的至少一种。The Mxene material according to claim 1 or 2, wherein the grafting agent is selected from N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid, N-(3-trimethoxysilylpropyl) ethylenediamine, N-(3-trimethoxysilylethyl)ethylenediamine, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, aminoethylamino At least one of isobutylmethyldimethoxysilane.
- 一种权利要求1~4任意一项所述的Mxene材料的制备方法，其特征在于，包括以下步骤：A preparation method of the Mxene material according to any one of claims 1 to 4, characterized in that, comprising the following steps:S1、将Mxene粉末分散于有机溶剂中得到悬浮液Ⅰ，再将接枝剂加入有机溶剂中得到溶液Ⅱ；S1. Disperse the Mxene powder in an organic solvent to obtain suspension I, and then add the grafting agent into the organic solvent to obtain solution II;S2、将溶液Ⅱ加入悬浮液Ⅰ中，在超声条件下搅拌反应，然后分离出固体，经清洗、干燥得到产物。S2. The solution II is added to the suspension I, and the reaction is stirred under ultrasonic conditions, and then the solid is separated, washed and dried to obtain the product.
- 根据权利要求5所述的方法，其特征在于，所述悬浮液Ⅰ的固含量为1~10 g/L，所述溶液Ⅱ的接枝剂浓度为2~10wt%。The method according to claim 5, wherein the solid content of the suspension I is 1-10 g/L, and the grafting agent concentration of the solution II is 2-10 wt%.
- 根据权利要求5所述的方法，其特征在于，所述S2中悬浮液Ⅰ和溶液Ⅱ的体积比为1：0.01~0.1。The method according to claim 5, wherein the volume ratio of the suspension I and the solution II in the S2 is 1:0.01-0.1.
- 根据权利要求5所述的方法，其特征在于，所述有机溶剂为乙醇或甲醇。The method according to claim 5, wherein the organic solvent is ethanol or methanol.
- 根据权利要求5所述的方法，其特征在于，所述清洗是依次用洗涤溶剂和水清洗，所述洗涤溶剂为甲醇、乙醇、乙二醇、丙酮、甲苯中的至少一种。The method according to claim 5, characterized in that, the cleaning is sequentially cleaning with a washing solvent and water, and the washing solvent is at least one of methanol, ethanol, ethylene glycol, acetone, and toluene.
- 根据权利要求5所述的方法，其特征在于，所述S2中反应的温度为50~80℃，反应的时间为5~15h。The method according to claim 5, wherein the temperature of the reaction in the S2 is 50-80°C, and the reaction time is 5-15h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110162357.XA CN113003675A (en) | 2021-02-05 | 2021-02-05 | Mxene material with organic chelating functional group grafted on surface and preparation method thereof |
| CN202110162357.X | 2021-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022165989A1 true WO2022165989A1 (en) | 2022-08-11 |
Family
ID=76383885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/087131 WO2022165989A1 (en) | 2021-02-05 | 2021-04-14 | Mxene material having organic chelating functional groups grafted on surface and preparation method therefor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113003675A (en) |
| WO (1) | WO2022165989A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117602690A (en) * | 2024-01-23 | 2024-02-27 | 神美科技有限公司 | Nonferrous metal mine flotation wastewater treatment agent and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113426428B (en) * | 2021-06-28 | 2022-04-29 | 武汉大学 | Polyaniline-sulfur nitrogen MXene/sodium alginate composite gel adsorbent and preparation method and application thereof |
| CN114160091A (en) * | 2021-12-02 | 2022-03-11 | 东北林业大学 | Preparation method of hydroxyl functionalized titanium carbide and application of hydroxyl functionalized titanium carbide in efficient adsorption and cesium removal |
| CN114503982B (en) * | 2021-12-10 | 2022-11-25 | 南京师范大学 | MXene- (g) -CP pesticide dispersant and preparation method thereof |
| CN114455690B (en) * | 2021-12-23 | 2023-01-31 | 南京师范大学 | Magnetic Mxene microbial carrier material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256611A (en) * | 2019-06-10 | 2019-09-20 | 中南大学 | A kind of application of MXene as radical initiator |
| CN111495220A (en) * | 2020-04-23 | 2020-08-07 | 厦门理工学院 | Preparation method of modified MXene two-dimensional layered material, modified microfiltration membrane and application |
| CN111545230A (en) * | 2020-04-23 | 2020-08-18 | 厦门理工学院 | Preparation method, product and application of nano titanium dioxide/MXene composite membrane |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587064A (en) * | 2016-12-22 | 2017-04-26 | 陕西科技大学 | Functionalized amino-titanium carbide and preparation method thereof |
| KR102266984B1 (en) * | 2019-04-08 | 2021-06-18 | 한국과학기술연구원 | 2-Dimensional MXene particles surface-modified with amines containing saturated or unsaturated hydrocarbons, the preparation method thereof and the use thereof |
| CN110801818B (en) * | 2019-10-25 | 2022-06-14 | 南昌大学 | Composite functional material for removing radioactive iodine and application thereof |
| CN111229314B (en) * | 2020-02-26 | 2022-09-30 | 淮阴师范学院 | Carboxyl aryl functionalized MXene material and preparation method and application thereof |
-
2021
- 2021-02-05 CN CN202110162357.XA patent/CN113003675A/en active Pending
- 2021-04-14 WO PCT/CN2021/087131 patent/WO2022165989A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256611A (en) * | 2019-06-10 | 2019-09-20 | 中南大学 | A kind of application of MXene as radical initiator |
| CN111495220A (en) * | 2020-04-23 | 2020-08-07 | 厦门理工学院 | Preparation method of modified MXene two-dimensional layered material, modified microfiltration membrane and application |
| CN111545230A (en) * | 2020-04-23 | 2020-08-18 | 厦门理工学院 | Preparation method, product and application of nano titanium dioxide/MXene composite membrane |
Non-Patent Citations (1)
| Title |
|---|
| JI JINGJING, ZHAO LUFANG, SHEN YANFEI, LIU SONGQIN, ZHANG YUANJIAN: "Covalent stabilization and functionalization of MXene via silylation reactions with improved surface properties", FLATCHEM, vol. 17, 1 September 2019 (2019-09-01), pages 1 - 6, XP055956948, ISSN: 2452-2627, DOI: 10.1016/j.flatc.2019.100128 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117602690A (en) * | 2024-01-23 | 2024-02-27 | 神美科技有限公司 | Nonferrous metal mine flotation wastewater treatment agent and preparation method thereof |
| CN117602690B (en) * | 2024-01-23 | 2024-03-22 | 神美科技有限公司 | Nonferrous metal mine flotation wastewater treatment agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113003675A (en) | 2021-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022165989A1 (en) | Mxene material having organic chelating functional groups grafted on surface and preparation method therefor | |
| Hasan et al. | A facile synthesis of poly (methyl methacrylate) grafted alginate@ Cys-bentonite copolymer hybrid nanocomposite for sequestration of heavy metals | |
| CN107442082B (en) | A kind of magnetism polyacrylamide/alginic acid zirconium gel ball and its preparation method and application | |
| Guo et al. | Synthesis of magnetic bioadsorbent for adsorption of Zn (II), Cd (II) and Pb (II) ions from aqueous solution | |
| CN105903438B (en) | A kind of attapulgite and the compound adsorbent and preparation method thereof of graphene oxide | |
| CN104190385A (en) | Polypyrrole/Fe3O4/graphene composite material, and preparation method and application thereof | |
| CN109745948B (en) | Cadmium-removing adsorbent, preparation method and application thereof | |
| Liu et al. | Mercury adsorption from aqueous solution by regenerated activated carbon produced from depleted mercury-containing catalyst by microwave-assisted decontamination | |
| CN113058549B (en) | Carbon nanosheet composite material and preparation method and application thereof | |
| Zhang et al. | Multifold enhanced synergistic removal of nickel and phosphate by a (N, Fe)-dual-functional bio-sorbent: Mechanism and application | |
| CN105603191B (en) | A kind of method of extracting vanadium from stone coal pickle liquor deacidification removal of impurities pretreatment | |
| Li et al. | In situ synthesis of novel peroxo-functionalized Ti3C2Tx adsorbent for aqueous pollutants removal: Role of oxygen-containing terminal groups | |
| CN111974366A (en) | Preparation and application of amphoteric carboxymethyl chitosan-based microspheres based on magnetic separation technology | |
| CN112978983A (en) | Iron-based biochar-based heavy metal complexing wastewater treatment and recycling process thereof | |
| Zhou et al. | Light induced growth of polyelectrolyte brushes on kaolinite surface with superior performance for capturing valuable rare-earth Ce3+ from wastewater | |
| Yang et al. | Mussel-inspired MgAl-LDH/carbon fiber film modified by polydopamine for highly efficient removal of Pb2+ | |
| CN111229167A (en) | Thiosemicarbazide modified magnetic graphene oxide adsorbent and preparation method and application thereof | |
| CN112169771A (en) | Preparation method of magnetic molasses hydrothermal carbon-based heavy metal adsorbent | |
| CN109046292B (en) | Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof | |
| Zhang et al. | Enhanced removal of hexavalent chromium from aqueous solution by functional polymer-wrapped gamma-alumina composite adsorbent | |
| CN113578256A (en) | Iron-magnesium hydrotalcite @ bentonite composite material and preparation method and application thereof | |
| CN103721689A (en) | Magnetic meso-porous silicon, preparation method of magnetic meso-porous silicon, magnetic meso-porous silicon adsorbent, preparation method and application of magnetic meso-porous silicon adsorbent | |
| Yang et al. | Recyclable hydrogel-MOFs composite beads for selective removal of Pb (II) from water | |
| CN105921128A (en) | Preparing method for magnetic hydrogel | |
| Zhao et al. | Versatile surface modification of ceramsite via honeycomb calcium-aluminum-silicate-hydrate and its functionalization by 3-thiocyanatopropyltriethoxysilane for enhanced cadmium (II) removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21923998 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21923998 Country of ref document: EP Kind code of ref document: A1 |