阅读说明：本技术 一种二维金属碳氮化物MXene的制备方法 (A kind of preparation method of two-dimensional metallic carbonitride MXene ) 是由 吴俊标 王誉 董琰峰 张霞 于 2019-08-29 设计创作，主要内容包括：本发明提供了一种二维金属碳氮化物MXene的制备方法,其步骤包括：将MAX相、DES相及刻蚀剂混合均匀得混合物料；将所述混合物料转移至反应釜中,在80～200℃的温度下反应6～48h得反应产物；反应釜自然冷却至室温,将反应产物用蒸馏水洗涤、过滤至滤液pH值为6～7,然后对过滤得到的沉淀用无水乙醇洗涤2-4次；将乙醇洗涤后的沉淀在50℃～100℃干燥温度下真空干燥4～48h,得到二维金属碳氮化物MXene。本发明提供的一种二维金属碳氮化物MXene的制备方法,安全性高、工艺简单、成本较低、环境友好且制备纯度高。(The present invention provides the preparation method of two-dimensional metallic carbonitride MXene a kind of, step includes: that MAX phase, DES phase and etching agent are uniformly mixed to obtain mixed material；The mixed material is transferred in reaction kettle, 80~200 DEG C at a temperature of reaction 6~48h obtain reaction product；Reaction kettle cooled to room temperature, it is 6~7 that reaction product, which is washed with distilled water, is filtered to filtrate pH value, is then washed 2-4 times to the precipitating being obtained by filtration with dehydrated alcohol；It will be deposited in 4~48h of vacuum drying under 50 DEG C~100 DEG C drying temperatures after ethanol washing, obtains two-dimensional metallic carbonitride MXene.The preparation method of two-dimensional metallic carbonitride MXene provided by the invention a kind of, highly-safe, simple process, cost is relatively low, environmental-friendly and preparation purity is high.)

1. a kind of preparation method of two-dimensional metallic carbonitride MXene, which comprises the steps of:

MAX phase, DES phase and etching agent are uniformly mixed to obtain mixed material；

The mixed material is transferred in reaction kettle, 80~200 DEG C at a temperature of reaction 6~48h obtain reaction product；

Reaction kettle cooled to room temperature, it is 6~7 that reaction product, which is washed with distilled water, is filtered to filtrate pH value, then to mistake Obtained precipitating is filtered to be washed 2-4 times with dehydrated alcohol；

It will be deposited in 4~48h of vacuum drying under 50 DEG C~100 DEG C drying temperatures after ethanol washing, obtains two-dimensional metallic carbon nitrogen Compound MXene.

2. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the MAX phase Middle M is one or more of transition metal element Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, Mo, A Al, Si, P, S, Ga, Ge, One or more of As, Cd, In, Sn, TI, Pb, X are C or/and N element, the atom number ratio of the M:A:X be 2:1:1, 3:1:2 or 4:1:3.

3. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the DES phase For the mixture of choline chloride and oxalic acid, the molar ratio of the choline chloride and oxalic acid is 1:0.25-4.

4. the preparation method of two-dimensional metallic carbonitride MXene according to claim 3, it is characterised in that: the chlorination The molar ratio of choline and oxalic acid is 1:0.5-2.

5. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the etching Agent is ammonium fluoride, and the molar ratio of the MAX phase and the ammonium fluoride is 1:1-20.

6. the preparation method of two-dimensional metallic carbonitride MXene according to claim 5, it is characterised in that: the MAX phase Molar ratio with the ammonium fluoride is 1:5-10.

7. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the reaction Temperature is 100-140 DEG C, and the reaction time is 12-36 hours.

8. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the drying Temperature is 60 DEG C~80 DEG C, and drying time is 8~16h.

9. the preparation method of two-dimensional metallic carbonitride MXene according to claim 8, it is characterised in that: the drying Time is 12h.

10. the preparation method of two-dimensional metallic carbonitride MXene according to claim 1, it is characterised in that: the reaction Reaction product in kettle can directly filter while hot to obtain filter residue and filtrate without cooling, the residue washing it is dry two-dimensional metallic Carbonitride MXene, the filtrate group are divided into DES phase and etchant mixture, can mix and be recycled with MAX again.

Technical field

The present invention relates to technical field of material, in particular to a kind of preparation side of two-dimensional metallic carbonitride MXene Method.

Background technique

Two-dimensional material includes graphene and graphene oxide (GO), graphite carbonitride (g-C₃N₄), transition metal curing Object (TMDs), the nanometer sheet metal organic framework (MOFs) of removing and zeolite nanometer sheet etc..Compared to block materials, two-dimensional material With unique laminar structured, to make it have unusual electricity, optically and mechanically performance.In past ten years In, two-dimensional material is by layer structure, film and the multifunctional composite as suitable structural motif building series.

2011, Yury Gogotsi et al., which is reported for the first time through selective etch strategy, prepared a kind of novel two Material titanium carbide is tieed up, MXene is named as.MXenes is family's transition metal carbide, nitride and carbonitride, common There is Ti₃C₂T_X,Ti₂CT_X,V₂CT_X,Mo₂CT_X,Cr₂CT_X,V₂CT_X,Ti ₂NT_X,Ti₃CNT_X,Ta₄C₃T_XDeng general formula M_n+1X_nT_X, Wherein M is transition metal (such as Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo etc.), and X is C or N element, and Tx represents functional group, such as Hydroxyl holds the functional groups such as oxygen or end group F.Up to now, there is the MXene two-dimensional material phase of more than 20 kinds of heterogeneities After successfully being prepared, preparation, property and the application of MXene has obtained extensive concern and the research of different field researcher, The development of this research field is greatly pushed.The chemical composition of multiplicity, structural configuration abundant, regulatable surface function The peculiar properties such as group and high intrinsic conductivity make MXenes have very big development prospect, including optical electrical in every field Catalysis, energy conversion and storage, photothermal conversion, chemical sensitisation, Water warfare and electromagnetic interference shield etc..

Currently, selectively chemical etching element A layer is still the main stream approach for synthesizing MXene from MAX phase, because of A Element is very active element, and metal M-A key is relatively weak compared to M-X key.Mainly make in current engraving method Make etchant with a large amount of hydrofluoric acid, such as uses the hydrofluoric acid solution (HF) or ammonium acid fluoride (NH of high concentration₄HF₂) or pass through Hydrochloric acid (HCl) and fluoride (such as LiF, NH₄F or FeF₃Deng) hydrofluoric acid that is formed in situ of high temperature hydro-thermal reaction.Nevertheless, hydrogen The extensive manufacture and its extensive use in energy related field that the high toxicity of fluoric acid but hinders MXene, because of hydrogen fluorine Acid is harmful to environment and can reduce material property (such as capacitor).In addition, hf etching is suitable for removal alkalinity/both sexes member Element is unable to etch acid element (for example, Zr₂Sulphur and V in SC₂The elements such as the phosphorus in PC).

Summary of the invention

Technical problem to be solved by the invention is to provide it is a kind of it is highly-safe, simple process, cost is relatively low, environmental-friendly And the preparation method of the two-dimensional metallic carbonitride MXene of preparation purity is high.

In order to solve the above technical problems, the present invention provides the preparation method of two-dimensional metallic carbonitride MXene a kind of, packet Include following steps:

MAX phase, DES phase and etching agent are uniformly mixed to obtain mixed material；

The mixed material is transferred in reaction kettle, 80~200 DEG C at a temperature of reaction 6~48h obtain reaction product；

Reaction kettle cooled to room temperature, it is 6~7 that reaction product, which is washed with distilled water, is filtered to filtrate pH value, then The precipitating being obtained by filtration is washed 2-4 times with dehydrated alcohol；

It will be deposited in 4~48h of vacuum drying under 50 DEG C~100 DEG C drying temperatures after ethanol washing, obtains two-dimensional metallic Carbonitride MXene.

Further, M is one of transition metal element Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, Mo in the MAX phase Or several, one or more of A Al, Si, P, S, Ga, Ge, As, Cd, In, Sn, TI, Pb, X be C or/and N element, it is described The atom number ratio of M:A:X is 2:1:1,3:1:2 or 4:1:3.

Further, the DES phase is the mixture of choline chloride and oxalic acid, the molar ratio of the choline chloride and oxalic acid For 1:0.25-4.

Preferably, the molar ratio of the choline chloride and oxalic acid is 1:0.5-2.

Further, the etching agent is ammonium fluoride, and the molar ratio of the MAX phase and the ammonium fluoride is 1:1-20.

Preferably, the MAX phase and the molar ratio of the ammonium fluoride are 1:5-10.

Preferably, the reaction temperature is 100-140 DEG C, and the reaction time is 12-36 hours.

Preferably, the drying temperature is 60 DEG C~80 DEG C, and drying time is 8~16h.

Preferably, the drying time is 12h.

Further, the reaction product in the reaction kettle can directly filter while hot to obtain filter residue and filtrate, institute without cooling It is dry that two-dimensional metallic carbonitride MXene, the filtrate group are divided into DES phase and etchant mixture to state residue washing, it can be again It mixes and is recycled with MAX.

The preparation method of two-dimensional metallic carbonitride MXene provided by the invention a kind of, uses under room temperature as solid phase ion Liquid does not have the method for water as reaction dissolvent, entire reaction system, substitutes at present with a large amount of high concentrations (40wt%) hydrofluoric acid As etching agent or use fluoride (LiF etc.) and concentrated hydrochloric acid under hydrothermal conditions in-situ preparation high concentration HF as the side of etching agent Method, can single step reaction can obtain final product, simple process, and can avoid the processing issuable splashing of high concentration of hydrofluoric acid Or topple over brought danger, safety greatly improves.Also, a kind of two-dimensional metallic carbonitride provided by the invention The preparation method of MXene, the DES phase for having used in raw material choline chloride and carboxylic acid to form, this makes DES phase have both ionic liquid It can be inserted into situ in MXene layers with the cation of the characteristic of molecular solvent, DES and expand interlamellar spacing, can be improved Mxene The performances such as chemical property, performance of the supercapacitor, and the group branch of DES phase makes to mix by interaction of hydrogen bond self-association The fusing point that object fusing point is lower than every kind of independent component is closed, react synthesis process can under normal pressure and lower temperature, from And security risk brought by conventional synthesis high temperature high pressure is avoided, adapt to clean technologies currently advocated and sustainable The requirement of development, and choline chloride in DES phase and oxalic acid are at low cost and be easy to get, and can reduce preparation cost.Meanwhile this The preparation method that a kind of two-dimensional metallic carbonitride MXene provided is provided, using ammonium fluoride as etching agent, in ammonium fluoride and The molar ratio of MAX is that 5:1 can be etched completely, and etching agent dosage is few, and the toxicity of reaction system is made to compare other with corrosivity Lithographic method is much smaller, and etching agent can also have the development prospect of recycling with the filtrate in preparation process, reduces Influence to environment, it is environmentally friendly.

Detailed description of the invention

Fig. 1 is a kind of flow chart of the preparation method of two-dimensional metallic carbonitride MXene provided in an embodiment of the present invention；

Fig. 2 is product X ray made from the preparation method of two-dimensional metallic carbonitride MXene provided in an embodiment of the present invention Diffracting spectrum；

Fig. 3 is sweeping for product made from the preparation method for the two-dimensional metallic carbonitride MXene that the embodiment of the present invention 1 provides Retouch electron microscope image；

Fig. 4 is sweeping for product made from the preparation method for the two-dimensional metallic carbonitride MXene that the embodiment of the present invention 2 provides Retouch electron microscope image；

Fig. 5 is sweeping for product made from the preparation method for the two-dimensional metallic carbonitride MXene that the embodiment of the present invention 3 provides Retouch electron microscope image；

Fig. 6 is sweeping for product made from the preparation method for the two-dimensional metallic carbonitride MXene that the embodiment of the present invention 4 provides Retouch electron microscope image.

Specific embodiment

Referring to Fig. 1, a kind of preparation method of two-dimensional metallic carbonitride MXene provided in an embodiment of the present invention, including such as Lower step:

MAX phase, DES phase and etching agent are uniformly mixed to obtain mixed material by step 1) according to a certain ratio.Wherein, MAX M is one or more of transition metal element Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, Mo in phase, A Al, Si, P, S, Ga, One or more of Ge, As, Cd, In, Sn, TI, Pb, X are C or/and N element, and the atom number ratio of the M:A:X is 2:1: 1,3:1:2 or 4:1:3.DES phase is the mixture of choline chloride and oxalic acid, and the molar ratio of choline chloride and oxalic acid is 1:0.25- 4, the molar ratio of choline chloride and oxalic acid is preferably 1:0.5-2.Etching agent is ammonium fluoride, and the molar ratio of MAX phase and ammonium fluoride is 1:1-20, preferred molar ratio are 1:5-10.

Mixed material is transferred in reaction kettle by step 2), and 6~48h is reacted under 80~200 DEG C of reaction temperatures to react Product.Preferred 100-140 DEG C of reaction temperature, the reaction time is 12-36 hours preferred.

For step 3) by reaction kettle cooled to room temperature, it is 6 that reaction product, which is washed with distilled water, is filtered to filtrate pH value ~7, then the precipitating being obtained by filtration is washed 2-4 times with dehydrated alcohol.

Step 4) by after ethanol washing being deposited under 50 DEG C~100 DEG C drying temperatures in a vacuum drying oven dry 4~ 48h obtains two-dimensional metallic carbonitride MXene.Wherein, preferably 60 DEG C~80 DEG C of drying temperature, drying time preferably 8~16h, Drying time more preferable 12h.

Certainly, as another embodiment of the invention, the reaction product reacted in the reaction kettle of step 2) It can directly be filtered to obtain filter residue and filtrate while hot without supercooling, two-dimensional metallic carbon is can be obtained into residue washing drying Nitride MXene.The group of the filtrate is divided into the mixture of DES phase and etching agent ammonium fluoride, and the mixture and MAX are mixed simultaneously After adding appropriate DES phase and etching agent ammonium fluoride, it is added to the etching reaction continued in reaction kettle next time, so that filtrate The DES phase and etching agent ammonium fluoride of middle remnants can be recycled, and can save DES phase and etching agent NH in this way₄The dosage of F, Save the cost, and influence of the etching agent to environment can be reduced.

A kind of preparation method of two-dimensional metallic carbonitride MXene provided by the invention is done below by specific embodiment It illustrates.