WO2019165806A1 - Method for preparing mxene nanosheet with mo vacancy - Google Patents

Method for preparing mxene nanosheet with mo vacancy Download PDF

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WO2019165806A1
WO2019165806A1 PCT/CN2018/117079 CN2018117079W WO2019165806A1 WO 2019165806 A1 WO2019165806 A1 WO 2019165806A1 CN 2018117079 W CN2018117079 W CN 2018117079W WO 2019165806 A1 WO2019165806 A1 WO 2019165806A1
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mxene
electrode
preparing
dispersion
vacancies
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French (fr)
Chinese (zh)
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吴文剑
赵玉飞
张美丽
蔡丽蓉
范洪波
汪国秀
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东莞理工学院
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
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    • C01B32/921—Titanium carbide
    • C—CHEMISTRY; METALLURGY
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    • C01B32/00—Carbon; Compounds thereof
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to the field of new materials technology, in particular to a method for preparing MXene nanosheets with Mo vacancies.
  • MXene is a new type of two-dimensional layered material, including transition metal carbides, nitrides and the like. Due to its excellent electrical conductivity, chemical stability and hydrophilicity, MXene exhibits excellent electrochemical performance in lithium/sodium ion batteries, lithium-sulfur batteries, supercapacitors, and water decomposition. Theoretical calculations indicate that the O-termination site of the MXene surface is the catalytically active site for the electrocatalytic hydrogen evolution reaction. However, the electrocatalytic activity of MXene prepared at present is not ideal. Therefore, screening MXene with better electrocatalytic activity and modifying it is the research hotspot of MXene in the field of electrocatalysis. Moreover, the current preparation of MXene nanosheets is mainly carried out by the intercalation of an organic solvent, however, this method generally requires relatively complicated steps and a low yield.
  • a method for preparing MXene nanosheets with Mo vacancies comprising the steps of:
  • the working electrode coated with the nano-dispersion liquid and the reference electrode and the counter electrode constitute a three-electrode system, and the pH of the electrolyte of the three-electrode system is 0-6;
  • Electrochemical stripping and activation of the applied voltage of the three-electrode system yielded MXene nanosheets with Mo vacancies.
  • FIG. 1 is a process flow diagram of a method for preparing an MXene nanosheet having Mo vacancies according to an embodiment
  • FIG. 2 is a schematic flow chart of a method for preparing a MXene nanosheet having Mo vacancies shown in FIG. 1;
  • Example 3 is a scanning electron micrograph of the Mo-containing MXene nanomaterial of Example 1 before (a), during peeling (b, c), and after peeling (d);
  • FIG. 4 is a schematic view showing a peeling process of a Mo-containing MXene nanomaterial corresponding to FIG. 3;
  • Example 5 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanomaterial prepared in Example 1;
  • Example 6 is a scanning transmission electron micrograph of a Mo 2 TiC 2 nanosheet prepared in Example 1;
  • Example 7 is an electrochemical activity diagram of a Mo 2 TiC 2 nanomaterial in Example 1 subjected to a constant potential scan;
  • Example 8 is a polarization curve of a cathode linear scan of a Mo 2 TiC 2 nanomaterial in Example 5, wherein (a) the number of scanning turns is 1, (b) the number of scanning turns is 100, and (c) the number of scanning cycles is 200, (d) the number of scanning circles is 1000, (e) the number of scanning circles is 1500, and (f) the number of scanning circles is 2000;
  • Example 9 is a polarization curve of a cathode linear scan of a Mo 2 TiC 2 nanosheet obtained by peeling off an organic solution in Example 10, and the number of scanning turns is 1.
  • a method for preparing an MXene nanosheet having Mo vacancies includes the following steps:
  • the precursors MAX and hydrofluoric acid (HF) are generally used as raw materials for the preparation of MXene nanomaterials.
  • the structure of the precursor MAX is generally M n+1 AX n , where M, A and X represent transition metals, respectively, IIIA or IVA Elemental, carbon or nitrogen.
  • the exposed faces of the upper and lower layers in the MAX structure are typically transition metals.
  • the process of preparing MXene from MAX generally requires more stringent synthesis conditions.
  • the commonly used method is to treat the precursor M n+1 AX n MAX with HF, and etch away the Al element in the MAX structure to obtain the corresponding MXene.
  • MXene which is currently widely prepared and studied, mainly includes Ti 2 C, V 2 C, Nb 2 C, Ti 3 C 2 , Nb 4 C 3 , Mo 2 C, and Mo 2 TiC 2 .
  • Theoretical calculations show that the MXene at the -O stop position is the catalytically active site for the electrocatalytic hydrogen evolution reaction.
  • the electrocatalytic activity of the currently prepared MXene is not ideal.
  • the alternative MXene for electrocatalytic hydrogen evolution reaction is mainly based on transition metal Mo as the main exposed surface, including Mo 2 C, Mo 2 TiC 2 , etc., which can improve the catalytic hydrogen evolution activity of MXene nanosheets.
  • the step of preparing the Mo-containing MXene nanomaterial comprises:
  • the precursor MAX is Mo 2 Ga 2 C or Mo 2 TiAlC 2 . Further, when the current body MAX is Mo 2 Ga 2 C, a Mo 2 C nano material is prepared; when the current body MAX is Mo 2 TiAlC 2 , a Mo 2 TiC 2 nano material is prepared.
  • the precursor MAX is in the form of a powder, and the precursor MAX is directly placed in an HF acid solution for heating and stirring.
  • the mass concentration of the HF acid solution is 30% to 50%.
  • the ratio of the precursor MAX to the HF acid is from 0.0167 g/mL to 0.2 g/mL.
  • the heating temperature is 35 to 55 ° C
  • the stirring rate during stirring is 100 to 400 rpm.
  • the lower solid was separated, and the lower solid was washed with water.
  • the lower solid is dispersed in water to wash the lower solid, and the solid is deposited by centrifugation, and the above operation is repeated until the supernatant obtained after centrifugation has a pH of 6-7.
  • the lower solid is dried in a freeze dryer at a temperature of from -30 ° C to -80 ° C and a pressure of from 10 Pa to 80 Pa.
  • the Mo-containing MXene nanomaterial is a Mo 2 TiC 2 nano material or a Mo 2 C nano material.
  • the Mo 2 TiC 2 nano material or the Mo 2 C nano material is prepared by the step S110.
  • the Mo 2 TiC 2 nano material or the Mo 2 C nano material may also be directly purchased. obtain.
  • the dispersion is selected from at least one of water, isopropanol, and ethanol. Further, the dispersion is a mixture of water and isopropyl alcohol or a mixture of water and ethanol. When the dispersion is a mixture of water and isopropanol, the volume ratio of water to isopropanol is 1:4 to 4:1; when the dispersion is a mixture of water and ethanol, the volume ratio of water to ethanol is 1:4 ⁇ 4:1.
  • the ratio of the Mo-containing MXene nanomaterial to the dispersion is from 1 mg/mL to 10 mg/mL.
  • the Mo-containing MXene nanomaterial is dispersed in the dispersion by ultrasonic dispersion, the ultrasonic dispersion power is 60 W to 100 W, and the ultrasonic dispersion time is 30 min to 90 min.
  • the working electrode is a glassy carbon electrode or a carbon paper electrode.
  • the glassy carbon electrode is purchased from a glassy carbon electrode of CHI Corporation, and the glassy carbon electrode has a diameter of 3 mm.
  • the carbon paper electrode is carbon paper.
  • the nanodispersion is applied directly to the surface of the working electrode, and the nanodispersion is applied to the working electrode in an amount of from 0.04 mg/cm 2 to 0.5 mg/cm 2 . Further, preferably, the coating amount of the nano-dispersion liquid on the glassy carbon electrode is 0.04 mg/cm 2 ; and the coating amount of the nano-dispersion liquid on the carbon paper electrode is 0.5 mg/cm 2 . Further, after coating the nano-dispersion on the working electrode, drying treatment is performed until the nano-dispersion is dried.
  • the nanodispersion is mixed with a binder solution and then dispensed onto the working electrode to enable the Mo-containing MXene nanomaterial to adhere to the working electrode.
  • the working electrode coated with the nano-dispersion liquid and the reference electrode and the counter electrode constitute a three-electrode system.
  • the reference electrode is a mercury sulphate electrode and the counter electrode is a carbon rod electrode. Further, the reference electrode is a mercury sulphate electrode purchased from China Gao Shi Ruilian, and the counter electrode is a carbon rod electrode purchased from China Gao Shi Ruilian.
  • the electrolyte is included in the three-electrode system.
  • the pH of the electrolyte is 0-6.
  • the electrolyte is selected from at least one of H 2 SO 4 , HCl, H 3 PO 4 , and HClO 4 .
  • the molar concentration of the electrolyte is from 0.01 M to 0.5 M.
  • the electrolyte has a great influence on the stripping of MXene nanomaterials.
  • the stripping effect of MXene nanomaterials decreases with the increase of the pH value of the electrolyte.
  • the MXene nanomaterial reacts with the alkaline solution to cause destruction of the structure of the MXene nanomaterial.
  • the voltage is applied to the electrochemical reaction by means of a constant potential sweep. Further, in the potentiostatic scanning mode, the potential is 100 mV vs RHE ⁇ 500 mV vs RHE, and the time for applying the voltage by the constant potential scanning is 2 h to 100 h.
  • a voltage is applied to the electrochemical reaction by means of a linear scan of the cathode.
  • the scanning range of the potential is 0 to -A mV vs RHE, wherein 400 ⁇ A ⁇ 550; the rate of potential scanning is 5 mV/s to 100 mV/s, and the number of turns of the potential scanning is 1000. Circle ⁇ 5000 laps.
  • the electrolyte is subjected to suction filtration treatment, and the solid is washed and freeze-dried.
  • a solid substance is obtained, and the solid precipitate is freeze-dried to obtain a MXene nanosheet having Mo vacancies.
  • the preparation method of the MXene nanosheet with Mo vacancies is carried out by electrochemical stripping to remove the MXene nano material containing Mo, which can completely strip the nanosheet material, avoid using a large amount of organic solvent, and the process is simpler and The yield is obviously improved.
  • MXene nanosheets with Mo vacancies can be prepared by using MXene nanomaterials containing Mo, and the surface properties can be controlled by electrochemical stripping to prepare MXene with a large number of Mo vacancies.
  • the nanosheets make the MXene nanosheets with Mo vacancies have better electrocatalytic hydrogen evolution reaction activity.
  • electrochemical stripping the surface oxidation of MXene nanomaterials can be avoided, and the -O termination position is maximized to further improve the catalytic activity of the electrocatalytic hydrogen evolution reaction.
  • MXene nanosheets with Mo vacancies prepared by the above-mentioned preparation method of Mo vacancies in the electrocatalytic hydrogen evolution reaction expands the application range of MXene and also provides more catalysts for electrocatalytic hydrogen evolution reaction.
  • MXene has very good conductivity and hydrophilicity.
  • the -O stop position on the surface is the catalytic active site of electrocatalytic hydrogen evolution reaction. Exposing more -O termination sites as much as possible can maximize the electrocatalytic hydrogen evolution. Reactivity, which not only extends the electrochemical application of MXene from energy storage to energy conversion, but also enriches the range of electrocatalytic hydrogen evolution catalysts.
  • the MXene nanosheets with Mo vacancies prepared by the above preparation method of MXene nanosheets with Mo vacancies can be used in the electrocatalytic hydrogen evolution reaction to enhance the catalytic hydrogen evolution reaction activity.
  • step S110 and step S160 may be omitted.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
  • the glassy carbon electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system.
  • the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.5 M, and the pH of the electrolyte is zero.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning.
  • the potential was -250 mV vs RHE, and the potentiometric scanning time was 25 h.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.08 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.1 M, and the pH of the electrolyte is 3.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning.
  • the potential was -100 mV vs RHE, and the potentiometric scanning time was 100 h.
  • the nano-dispersion was applied to a carbon paper electrode, and the coating amount of the nano-dispersion on the carbon paper electrode was 0.5 mg/cm 2 .
  • the carbon paper electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system.
  • the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.05 M, and the pH of the electrolyte is 4.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning.
  • the potential was -500 mV vs RHE, and the potentiometric scanning time was 2 h.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.08 mg/cm 2 .
  • the glassy carbon electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system.
  • the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.5 M, and the pH of the electrolyte is zero.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning.
  • the potential was -450 mV vs RHE, and the potentiometric scanning time was 48 h.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.05 M, and the pH of the electrolyte is 4.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of cathode linear scanning.
  • the potential scanning range was 0--400 mV vs RHE, the potential scanning rate was 5 mV/s, and the potential scanning circle was 2000. ring.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.1 M, and the pH of the electrolyte is 3.
  • Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning wherein the potential scanning range is 0--550 mV vs RHE, the potential scanning rate is 100 mV/s, and the potential scanning circle is 2000. ring.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.01 M, and the pH of the electrolyte is 6.
  • Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning wherein the potential scanning range is 0--500 mV vs RHE, the potential scanning rate is 50 mV/s, and the potential scanning circle is 3000. ring.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a phosphate buffer solution, and the pH of the electrolyte is 7.
  • Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning.
  • the potential was -100 mV vs RHE, and the potentiometric scanning time was 100 h.
  • the nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.06 mg/cm 2 .
  • the above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a KOH solution having a molar concentration of 1 M, and the pH of the electrolyte is 12.
  • Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning wherein the potential scanning range is 0--550 mV vs RHE, the potential scanning rate is 100 mV/s, and the potential scanning circle is 2000. ring.
  • the MXene nanomaterials containing Mo before, during, and after stripping of Example 1 were subjected to scanning electron microscopy. The results are shown in FIG. Among them, the scanning electron microscope test was carried out by using a scanning electron microscope tester of the type Zeiss Supra 55VP.
  • the Mo 2 TiC 2 nanomaterials prepared in Example 1 and the Mo 2 TiC 2 nanosheets were respectively subjected to scanning transmission electron microscopy, and the results are shown in FIGS. 5 and 6.
  • the scanning electron microscope test was carried out by using a scanning electron microscope (STEM) model of STEM, JEOL JEM-ARM200F.
  • Example 5 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanomaterial prepared in Example 1. It can be seen from the figure that the Al atom layer is removed during the HF treatment, and the Ti atom layer is sandwiched by two layers of Mo atoms. in the middle.
  • Example 6 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanosheet prepared in Example 1. After electrocatalytic activation, atomic defects, that is, Mo vacancies, were observed on the Mo 2 TiC 2 nanosheet.
  • Example 7 is an electrochemical activity diagram of the Mo 2 TiC 2 nanomaterial in Example 1 subjected to constant potential scanning. During the potentiostatic scanning process, the current density can be observed to increase sharply in the first 10 hours, and gradually tend to be in the first 15 hours. stable.
  • Example 8 is a polarization curve of a Mo 2 TiC 2 nanomaterial in a cathode linear scan in Example 5.
  • the current density increases, after 1000 cycles. becoming steady.
  • Mo 2 TiC 2 MXene during the scanning process as the number of turns scanning electrochemical properties of hydrogen is gradually increased, reached a maximum at the time of 1000 cycles, after which the catalytic activity stable.
  • the improvement in performance during hydrogen evolution is mainly due to the electrochemical stripping of Mo 2 TiC 2 MXene.
  • Mo 2 TiC 2 nanosheets exposed more catalytically active surfaces and caused a large amount of Mo vacancies during electrochemical stripping.
  • Fig. 9 is a graph showing the electrocatalytic hydrogen evolution performance of a Mo 2 TiC 2 nanosheet obtained by peeling off with an organic solvent in Example 10.
  • This catalytic activity is relatively low, compared to Mo 2 TiC 2 MXene and electrochemically stripped Mo 2 TiC 2 nanosheets.
  • the main reason is that some of the organic solvent used in the stripping process remains on the surface of the Mo 2 TiC 2 nanosheet, and a certain bond is formed between the surface group, such as the O-termination site and the OH-termination site. The binding to H 3 O + in the solution is blocked, thereby reducing the catalytic hydrogen evolution reaction activity.

Abstract

A method for preparing a MXene nanosheet with Mo vacancy, comprising the steps of: dispersing a Mo-containing MXene nano material in a dispersing liquid to obtain a nano dispersion liquid; coating the nano dispersion liquid onto a working electrode; constituting the working electrode coated with the nano dispersion liquid, a reference electrode and a counter electrode into a three-electrode system, the pH value of the electrolytic solution of the three-electrode system being 0 to 6; and applying a voltage to the three-electrode system to perform electrochemical stripping and activation so as to obtain a MXene nanosheet having Mo vacancy.

Description

具有Mo空位的MXene纳米片的制备方法Method for preparing MXene nanosheet with Mo vacancy 技术领域Technical field
本发明涉及新材料技术领域，特别是涉及具有Mo空位的MXene纳米片的制备方法。The invention relates to the field of new materials technology, in particular to a method for preparing MXene nanosheets with Mo vacancies.
背景技术Background technique
MXene是一种新型的二维层状材料，包括过渡金属碳化物，氮化物等。由于其具有优异的导电性，化学稳定性和亲水性，MXene在锂/钠离子电池，锂硫电池，超级电容器，水分解等领域表现出了优异的电化学性能。理论计算表明MXene表面的O-终止位是电催化析氢反应的催化活性位点。然而，目前制备得到的MXene的电催化活性都不太理想，因此，筛选出具有较好的电催化活性的MXene，并对其进行改性是目前研究MXene在电催化领域的研究热点。并且，目前MXene纳米片的制备主要是利用有机溶剂的嵌入从而进行剥离，然而，此方法一般需要较为复杂的步骤，且产率较低。MXene is a new type of two-dimensional layered material, including transition metal carbides, nitrides and the like. Due to its excellent electrical conductivity, chemical stability and hydrophilicity, MXene exhibits excellent electrochemical performance in lithium/sodium ion batteries, lithium-sulfur batteries, supercapacitors, and water decomposition. Theoretical calculations indicate that the O-termination site of the MXene surface is the catalytically active site for the electrocatalytic hydrogen evolution reaction. However, the electrocatalytic activity of MXene prepared at present is not ideal. Therefore, screening MXene with better electrocatalytic activity and modifying it is the research hotspot of MXene in the field of electrocatalysis. Moreover, the current preparation of MXene nanosheets is mainly carried out by the intercalation of an organic solvent, however, this method generally requires relatively complicated steps and a low yield.
发明内容Summary of the invention
基于此，有必要针对目前制备得到的MXene的电催化活性不太理想，且采用有机溶剂嵌入MXene材料进行剥离的方式步骤复杂，且产率较低的问题，提供一种具有Mo空位的MXene纳米片的制备方法。Based on this, it is necessary to aim at the electrocatalytic activity of the currently prepared MXene, and the method of using the organic solvent to embed the MXene material for stripping is complicated, and the yield is low, and the MXene nanometer with Mo vacancies is provided. The preparation method of the tablet.
一种具有Mo空位的MXene纳米片的制备方法，包括步骤：A method for preparing MXene nanosheets with Mo vacancies, comprising the steps of:
将含Mo的MXene纳米材料分散于分散液中得到纳米分散液；Dispersing the Mo-containing MXene nano material in the dispersion to obtain a nano-dispersion liquid;
将所述纳米分散液涂覆于工作电极上；Applying the nanodispersion to a working electrode;
将所述涂覆有纳米分散液的工作电极与参比电极及对电极组成三电极体系，所述三电极体系的电解液的pH值为0～6；及The working electrode coated with the nano-dispersion liquid and the reference electrode and the counter electrode constitute a three-electrode system, and the pH of the electrolyte of the three-electrode system is 0-6;
对所述三电极体系外加电压进行电化学剥离和活化得到具有Mo空位的MXene纳米片。Electrochemical stripping and activation of the applied voltage of the three-electrode system yielded MXene nanosheets with Mo vacancies.
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。Details of one or more embodiments of the invention are set forth in the accompanying drawings and description below. Other features, objects, and advantages of the invention will be apparent from the description and appended claims.
附图说明DRAWINGS
图1为一实施方式的具有Mo空位的MXene纳米片的制备方法的工艺流程图；1 is a process flow diagram of a method for preparing an MXene nanosheet having Mo vacancies according to an embodiment;
图2为图1所示的具有Mo空位的MXene纳米片的制备方法的流程示意图；2 is a schematic flow chart of a method for preparing a MXene nanosheet having Mo vacancies shown in FIG. 1;
图3为实施例1中含Mo的MXene纳米材料在剥离前(a)、剥离中(b、c)和剥离后(d)的扫描电镜照片；3 is a scanning electron micrograph of the Mo-containing MXene nanomaterial of Example 1 before (a), during peeling (b, c), and after peeling (d);
图4为与图3对应的含Mo的MXene纳米材料剥离过程的示意图；4 is a schematic view showing a peeling process of a Mo-containing MXene nanomaterial corresponding to FIG. 3;
图5为实施例1中制备得到的Mo 2TiC 2纳米材料扫描透射电镜照片； 5 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanomaterial prepared in Example 1;
图6为实施例1中制备得到的Mo 2TiC 2纳米片的扫描透射电镜照片； 6 is a scanning transmission electron micrograph of a Mo 2 TiC 2 nanosheet prepared in Example 1;
图7为实施例1中Mo 2TiC 2纳米材料在进行恒电位扫描的电化学活性图； 7 is an electrochemical activity diagram of a Mo 2 TiC 2 nanomaterial in Example 1 subjected to a constant potential scan;
图8为实施例5中Mo 2TiC 2纳米材料在进行阴极线性扫描的极化曲线，其中，(a)扫描圈数为1，(b)扫描圈数为100，(c)扫描圈数为200，(d)扫描圈数为1000，(e)扫描圈数为1500，(f)扫描圈数为2000； 8 is a polarization curve of a cathode linear scan of a Mo 2 TiC 2 nanomaterial in Example 5, wherein (a) the number of scanning turns is 1, (b) the number of scanning turns is 100, and (c) the number of scanning cycles is 200, (d) the number of scanning circles is 1000, (e) the number of scanning circles is 1500, and (f) the number of scanning circles is 2000;
图9为实施例10中采用有机溶液剥离得到的Mo 2TiC 2纳米片进行阴极线性扫描的极化曲线，扫描圈数为1。 9 is a polarization curve of a cathode linear scan of a Mo 2 TiC 2 nanosheet obtained by peeling off an organic solution in Example 10, and the number of scanning turns is 1.
具体实施方式Detailed ways
下面将结合具体实施方式及附图对具有Mo空位的MXene纳米片的制备方法做进一步的详细说明。The preparation method of the MXene nanosheet having Mo vacancies will be further described in detail below with reference to the specific embodiments and the accompanying drawings.
请参阅图1，一实施方式的具有Mo空位的MXene纳米片的制备方法包括以下步骤：Referring to FIG. 1, a method for preparing an MXene nanosheet having Mo vacancies according to an embodiment includes the following steps:
S110、制备含Mo的MXene纳米材料。S110. Preparing a MXene nano material containing Mo.
制备MXene纳米材料一般采用前驱体MAX和氢氟酸(HF)作为原材料，前驱体MAX的结构式一般为M n+1AX n，其中M，A和X分别代表过渡金属，IIIA或者IVA族的主要元素、碳或者氮元素。MAX结构中的上下层暴露的面一般是过渡金属。由MAX制备MXene的过程一般需要较为严苛的合成条件，常用的方法是利用HF对其前驱体M n+1AX nMAX进行处理，腐蚀掉MAX结构中的Al元素，得到相对应的MXene。在腐蚀的过程中，MXene的过渡金属表面会被-O、-OH或者-F元素所取代。目前得到广泛制备和研究的MXene主要包括Ti 2C、V 2C、Nb 2C、Ti 3C 2、Nb 4C 3、Mo 2C和Mo 2TiC 2等。理论计算表明，-O终止位的MXene是电催化析氢反应的催化活性位点。然而目前制备得到的MXene的电催化活性都不太理想。可选择的用于电催化析氢反应的MXene主要是以过渡金属Mo为主要暴露面，包括Mo 2C，Mo 2TiC 2等，可以提高MXene纳米片的催化析氢活性。 The precursors MAX and hydrofluoric acid (HF) are generally used as raw materials for the preparation of MXene nanomaterials. The structure of the precursor MAX is generally M n+1 AX n , where M, A and X represent transition metals, respectively, IIIA or IVA Elemental, carbon or nitrogen. The exposed faces of the upper and lower layers in the MAX structure are typically transition metals. The process of preparing MXene from MAX generally requires more stringent synthesis conditions. The commonly used method is to treat the precursor M n+1 AX n MAX with HF, and etch away the Al element in the MAX structure to obtain the corresponding MXene. During the etching process, the transition metal surface of MXene is replaced by -O, -OH or -F elements. MXene, which is currently widely prepared and studied, mainly includes Ti 2 C, V 2 C, Nb 2 C, Ti 3 C 2 , Nb 4 C 3 , Mo 2 C, and Mo 2 TiC 2 . Theoretical calculations show that the MXene at the -O stop position is the catalytically active site for the electrocatalytic hydrogen evolution reaction. However, the electrocatalytic activity of the currently prepared MXene is not ideal. The alternative MXene for electrocatalytic hydrogen evolution reaction is mainly based on transition metal Mo as the main exposed surface, including Mo 2 C, Mo 2 TiC 2 , etc., which can improve the catalytic hydrogen evolution activity of MXene nanosheets.
在其中一个实施方式中，制备含Mo的MXene纳米材料的步骤包括：In one embodiment, the step of preparing the Mo-containing MXene nanomaterial comprises:
S111、将前驱体MAX加入到HF酸中在35℃～55℃的温度下反应24h～48h得到反应液。S111, adding the precursor MAX to the HF acid and reacting at a temperature of 35 ° C to 55 ° C for 24 to 48 hours to obtain a reaction liquid.
在其中一个实施方式中，前驱体MAX为Mo 2Ga 2C或Mo 2TiAlC 2。进一 步地，当前驱体MAX为Mo 2Ga 2C时，制备得到Mo 2C纳米材料；当前驱体MAX为Mo 2TiAlC 2时，制备得到Mo 2TiC 2纳米材料。 In one embodiment, the precursor MAX is Mo 2 Ga 2 C or Mo 2 TiAlC 2 . Further, when the current body MAX is Mo 2 Ga 2 C, a Mo 2 C nano material is prepared; when the current body MAX is Mo 2 TiAlC 2 , a Mo 2 TiC 2 nano material is prepared.
在其中一个实施方式中，前驱体MAX为粉末状，直接将前驱体MAX置于HF酸溶液中进行加热搅拌。HF酸溶液的质量浓度为30％～50％。在其中一个实施方式中，前驱体MAX与HF酸的用量比为0.0167g/mL～0.2g/mL。In one embodiment, the precursor MAX is in the form of a powder, and the precursor MAX is directly placed in an HF acid solution for heating and stirring. The mass concentration of the HF acid solution is 30% to 50%. In one embodiment, the ratio of the precursor MAX to the HF acid is from 0.0167 g/mL to 0.2 g/mL.
在其中一个实施方式中，进行加热的温度为35℃～55℃，进行搅拌时的搅拌速率为100rpm～400rpm。In one embodiment, the heating temperature is 35 to 55 ° C, and the stirring rate during stirring is 100 to 400 rpm.
S112、将反应液进行离心后对下层固体进行洗涤至上层清液的pH值为6～7。S112. After centrifuging the reaction solution, the lower layer solid is washed until the pH of the supernatant liquid is 6-7.
将反应液进行离心后将下层固体分离出来，并用水对下层固体进行洗涤。在其中一个实施方式中，将下层固体分散在水中以对下层固体进行洗涤，再通过离心的方式使得固体沉积，重复上述操作至离心后得到的上层清液的pH值为6～7。After the reaction solution was centrifuged, the lower solid was separated, and the lower solid was washed with water. In one embodiment, the lower solid is dispersed in water to wash the lower solid, and the solid is deposited by centrifugation, and the above operation is repeated until the supernatant obtained after centrifugation has a pH of 6-7.
S113、对下层固体进行冷冻干燥得到MXene纳米材料。S113, lyophilizing the underlying solid to obtain MXene nanomaterial.
在其中一个实施方式中，在冷冻干燥机中对下层固体进行干燥处理，干燥处理的温度为-30℃～-80℃，压力为10Pa～80Pa。In one embodiment, the lower solid is dried in a freeze dryer at a temperature of from -30 ° C to -80 ° C and a pressure of from 10 Pa to 80 Pa.
S120、将含Mo的MXene纳米材料分散于分散液中得到纳米分散液。S120, dispersing Mo-containing MXene nano material in a dispersion to obtain a nano-dispersion liquid.
在其中一个实施方式中，含Mo的MXene纳米材料为Mo 2TiC 2纳米材料或Mo 2C纳米材料。在本实施方式中，Mo 2TiC 2纳米材料或Mo 2C纳米材料通过步骤S110制备得到，在其他实施方式中，Mo 2TiC 2纳米材料或Mo 2C纳米材料也可以直接采用外购的方式获得。 In one embodiment, the Mo-containing MXene nanomaterial is a Mo 2 TiC 2 nano material or a Mo 2 C nano material. In this embodiment, the Mo 2 TiC 2 nano material or the Mo 2 C nano material is prepared by the step S110. In other embodiments, the Mo 2 TiC 2 nano material or the Mo 2 C nano material may also be directly purchased. obtain.
在其中一个实施方式中，分散液选自水、异丙醇和乙醇中的至少一种。进一步地，分散液为水和异丙醇的混合液或水和乙醇的混合液。当分散液为 水和异丙醇的混合液时，水和异丙醇的体积比为1:4～4:1；当分散液为水和乙醇的混合液时，水和乙醇的体积比为1:4～4:1。In one embodiment, the dispersion is selected from at least one of water, isopropanol, and ethanol. Further, the dispersion is a mixture of water and isopropyl alcohol or a mixture of water and ethanol. When the dispersion is a mixture of water and isopropanol, the volume ratio of water to isopropanol is 1:4 to 4:1; when the dispersion is a mixture of water and ethanol, the volume ratio of water to ethanol is 1:4~4:1.
在其中一个实施方式中，将含Mo的MXene纳米材料分散于分散液中时，含Mo的MXene纳米材料与分散液的用量比为1mg/mL～10mg/mL。In one embodiment, when the Mo-containing MXene nanomaterial is dispersed in the dispersion, the ratio of the Mo-containing MXene nanomaterial to the dispersion is from 1 mg/mL to 10 mg/mL.
在其中一个实施方式中，将含Mo的MXene纳米材料分散于分散液中是采用超声波分散的方式进行，超声波分散的功率为60W～100W，超声波分散的时间为30min～90min。In one embodiment, the Mo-containing MXene nanomaterial is dispersed in the dispersion by ultrasonic dispersion, the ultrasonic dispersion power is 60 W to 100 W, and the ultrasonic dispersion time is 30 min to 90 min.
S130、将纳米分散液涂覆于工作电极上。S130. Applying the nano dispersion to the working electrode.
在其中一个实施方式中，工作电极为玻碳电极或碳纸电极。在其中一个实施方式中，玻碳电极购自CHI公司的玻碳电极，玻碳电极的直径为3mm。碳纸电极为碳纸。In one embodiment, the working electrode is a glassy carbon electrode or a carbon paper electrode. In one embodiment, the glassy carbon electrode is purchased from a glassy carbon electrode of CHI Corporation, and the glassy carbon electrode has a diameter of 3 mm. The carbon paper electrode is carbon paper.
在其中一个实施方式中，将纳米分散液直接涂覆于工作电极的表面，纳米分散液在工作电极上的涂覆量为0.04mg/cm 2～0.5mg/cm 2。进一步地，优选地，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2；纳米分散液在碳纸电极上的涂覆量为0.5mg/cm 2。进一步地，在工作电极上涂覆纳米分散液后进行干燥处理至纳米分散液干燥。 In one embodiment, the nanodispersion is applied directly to the surface of the working electrode, and the nanodispersion is applied to the working electrode in an amount of from 0.04 mg/cm 2 to 0.5 mg/cm 2 . Further, preferably, the coating amount of the nano-dispersion liquid on the glassy carbon electrode is 0.04 mg/cm 2 ; and the coating amount of the nano-dispersion liquid on the carbon paper electrode is 0.5 mg/cm 2 . Further, after coating the nano-dispersion on the working electrode, drying treatment is performed until the nano-dispersion is dried.
在其他实施方式中，将纳米分散液与粘合剂溶液混合，再滴涂到工作电极上，使得含Mo的MXene纳米材料能够粘附于工作电极上。In other embodiments, the nanodispersion is mixed with a binder solution and then dispensed onto the working electrode to enable the Mo-containing MXene nanomaterial to adhere to the working electrode.
S140、将涂覆有纳米分散液的工作电极与参比电极及对电极组成三电极体系。S140. The working electrode coated with the nano-dispersion liquid and the reference electrode and the counter electrode constitute a three-electrode system.
在其中一个实施方式中，参比电极为硫酸亚汞电极，对电极为碳棒电极。进一步地，参比电极为购自中国高仕睿联的硫酸亚汞电极，对电极为购自中国高仕睿联的碳棒电极。In one embodiment, the reference electrode is a mercury sulphate electrode and the counter electrode is a carbon rod electrode. Further, the reference electrode is a mercury sulphate electrode purchased from China Gao Shi Ruilian, and the counter electrode is a carbon rod electrode purchased from China Gao Shi Ruilian.
在其中一个实施方式中，三电极体系中包括电解液。电解液的pH值为0～6。In one of the embodiments, the electrolyte is included in the three-electrode system. The pH of the electrolyte is 0-6.
在其中一个实施方式中，电解液选自H 2SO 4、HCl、H 3PO 4和HClO 4中的至少一种。电解液的摩尔浓度为0.01M～0.5M。 In one embodiment, the electrolyte is selected from at least one of H 2 SO 4 , HCl, H 3 PO 4 , and HClO 4 . The molar concentration of the electrolyte is from 0.01 M to 0.5 M.
需要说明的是，在三电极体系中，电解液对MXene纳米材料的剥离具有很大的影响，通过大量实验发现随着电解液的pH值增大，MXene纳米材料的剥离效果逐渐降低。而在中性溶液中基本没有剥离效果，而在碱性溶液中MXene纳米材料会与碱性溶液发生反应导致MXene纳米材料结构的破坏。It should be noted that in the three-electrode system, the electrolyte has a great influence on the stripping of MXene nanomaterials. Through a large number of experiments, it is found that the stripping effect of MXene nanomaterials decreases with the increase of the pH value of the electrolyte. However, there is substantially no peeling effect in the neutral solution, and in the alkaline solution, the MXene nanomaterial reacts with the alkaline solution to cause destruction of the structure of the MXene nanomaterial.
S150、对三电极体系外加电压进行电化学反应。S150, performing electrochemical reaction on the applied voltage of the three-electrode system.
在其中一个实施方式中，采用恒电位扫描的方式外加电压进行电化学反应。进一步地，恒电位扫描的方式中电位为100mV vs RHE～500mV vs RHE，采用恒电位扫描的方式外加电压进行电化学反应的时间为2h～100h。In one embodiment, the voltage is applied to the electrochemical reaction by means of a constant potential sweep. Further, in the potentiostatic scanning mode, the potential is 100 mV vs RHE ～500 mV vs RHE, and the time for applying the voltage by the constant potential scanning is 2 h to 100 h.
在另一个实施方式中，采用阴极线性扫描的方式外加电压进行电化学反应。进一步地，阴极线性扫描的方式中电位的扫描范围为0～-A mV vs RHE，其中，400≤A≤550；电位扫描的速率为5mV/s～100mV/s，电位扫描的圈数为1000圈～5000圈。In another embodiment, a voltage is applied to the electrochemical reaction by means of a linear scan of the cathode. Further, in the mode of linear scanning of the cathode, the scanning range of the potential is 0 to -A mV vs RHE, wherein 400≤A≤550; the rate of potential scanning is 5 mV/s to 100 mV/s, and the number of turns of the potential scanning is 1000. Circle ~ 5000 laps.
S160、对电解液进行抽滤处理并对固体进行洗涤和冷冻干燥。S160. The electrolyte is subjected to suction filtration treatment, and the solid is washed and freeze-dried.
在其中一个实施方式中，对电解液进行抽滤处理后，得到固体物质，再对固体沉淀进行冷冻干燥从而得到具有Mo空位的MXene纳米片。In one embodiment, after the electrolytic solution is subjected to suction filtration treatment, a solid substance is obtained, and the solid precipitate is freeze-dried to obtain a MXene nanosheet having Mo vacancies.
上述具有Mo空位的MXene纳米片的制备方法，采用电化学剥离的方式对含有Mo的MXene纳米材料进行剥离，可以实现纳米片层材料的完全剥离，避免了大量使用有机溶剂，工艺更为简单且产率明显提高；另外，采用含有Mo的MXene纳米材料，能够制备得到具有Mo空位的MXene纳米片，且采 用电化学的方式进行剥离能够对其表面特性进行调控以制备得到具有大量Mo空位的MXene纳米片，使得具有Mo空位的MXene纳米片具有更好的电催化析氢反应活性。另外，采用电化学剥离的方式，能够避免MXene纳米材料的表面氧化，并最大限度的暴露-O终止位，以进一步提高电催化析氢反应的催化活性。The preparation method of the MXene nanosheet with Mo vacancies is carried out by electrochemical stripping to remove the MXene nano material containing Mo, which can completely strip the nanosheet material, avoid using a large amount of organic solvent, and the process is simpler and The yield is obviously improved. In addition, MXene nanosheets with Mo vacancies can be prepared by using MXene nanomaterials containing Mo, and the surface properties can be controlled by electrochemical stripping to prepare MXene with a large number of Mo vacancies. The nanosheets make the MXene nanosheets with Mo vacancies have better electrocatalytic hydrogen evolution reaction activity. In addition, by electrochemical stripping, the surface oxidation of MXene nanomaterials can be avoided, and the -O termination position is maximized to further improve the catalytic activity of the electrocatalytic hydrogen evolution reaction.
上述具有Mo空位的MXene纳米片的制备方法制备得到的具有Mo空位的MXene纳米片在电催化析氢反应中的应用，扩展了MXene的应用范围，同时也为电催化析氢反应提供了更多的催化剂的选择。MXene具有非常好的导电性和亲水性，其表面的-O终止位是电催化析氢反应的催化活性位点，尽可能的暴露更多的-O终止位可以最大限度的提高其电催化析氢反应活性，这不仅将MXene的电化学应用从储能的角度拓展到了能量转换，还丰富了电催化析氢反应催化剂的范围。The application of the MXene nanosheets with Mo vacancies prepared by the above-mentioned preparation method of Mo vacancies in the electrocatalytic hydrogen evolution reaction expands the application range of MXene and also provides more catalysts for electrocatalytic hydrogen evolution reaction. s Choice. MXene has very good conductivity and hydrophilicity. The -O stop position on the surface is the catalytic active site of electrocatalytic hydrogen evolution reaction. Exposing more -O termination sites as much as possible can maximize the electrocatalytic hydrogen evolution. Reactivity, which not only extends the electrochemical application of MXene from energy storage to energy conversion, but also enriches the range of electrocatalytic hydrogen evolution catalysts.
上述具有Mo空位的MXene纳米片的制备方法制备得到的具有Mo空位的MXene纳米片能够在电催化析氢反应中应用，以提高催化析氢反应活性。The MXene nanosheets with Mo vacancies prepared by the above preparation method of MXene nanosheets with Mo vacancies can be used in the electrocatalytic hydrogen evolution reaction to enhance the catalytic hydrogen evolution reaction activity.
需要说明的是，在其他实施方式中，步骤S110、步骤S160也可以省略。It should be noted that in other embodiments, step S110 and step S160 may be omitted.
下面为具体实施例的说明，以下实施例如无特殊说明，则不含有除不可避免的杂质以外的其他未明确指出的组分。The following is a description of specific examples, and the following examples, unless otherwise specified, do not contain other components not specifically indicated except for unavoidable impurities.
实施例1Example 1
(1)将0.5g的Mo 2TiAlC 2加入到10mL的质量浓度为50％的HF酸溶液中，加热至35℃下反应48h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行冷冻干燥得到Mo 2TiC 2纳米材料。 (1) Add 0.5 g of Mo 2 TiAlC 2 to 10 mL of a 50% by mass HF acid solution, heat to 35 ° C for 48 h to obtain a reaction solution, centrifuge the reaction solution, and wash the lower layer of solid to the supernatant. When the pH of the liquid was 6, the lower layer solid was freeze-dried to obtain a Mo 2 TiC 2 nanomaterial.
(2)取4mg的Mo 2TiC 2纳米材料分散于1mL的分散液中得到纳米分散 液，其中分散液为体积比为1:1的水和异丙醇的混合液。 (2) 4 mg of Mo 2 TiC 2 nanomaterial was dispersed in 1 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and isopropyl alcohol in a volume ratio of 1:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.5M的H 2SO 4溶液，电解液的pH值为0。 (4) The glassy carbon electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system. The electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.5 M, and the pH of the electrolyte is zero.
(5)采用恒电位扫描的方式对三电极体系外加电压进行电化学反应，其中，电位为-250mV vs RHE，恒电位扫描的时间为25h。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning. The potential was -250 mV vs RHE, and the potentiometric scanning time was 25 h.
(6)对电解液进行抽滤处理并对固体沉淀进行洗涤和冷冻干燥得到Mo 2TiC 2纳米片。 (6) The electrolytic solution was subjected to suction filtration treatment, and the solid precipitate was washed and freeze-dried to obtain a Mo 2 TiC 2 nanosheet.
实施例2Example 2
(1)将0.5g的Mo 2TiAlC 2加入到30mL的质量浓度为35％的HF酸溶液中，加热至55℃下反应24h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为7时，对下层固体进行干燥和研磨得到Mo 2TiC 2纳米材料。 (1) 0.5 g of Mo 2 TiAlC 2 was added to 30 mL of a 35% by mass HF acid solution, and heated to 55 ° C for 24 hours to obtain a reaction solution. After centrifuging the reaction solution, the lower layer of solid was washed to the supernatant. When the pH of the liquid is 7, the underlying solid is dried and ground to obtain a Mo 2 TiC 2 nanomaterial.
(2)取10mg的Mo 2TiC 2纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为1:4的水和乙醇的混合液。 (2) 10 mg of Mo 2 TiC 2 nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and ethanol in a volume ratio of 1:4.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.08mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.08 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.1M的H 2SO 4溶液，电解液的pH值为3。 (4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.1 M, and the pH of the electrolyte is 3.
(5)采用恒电位扫描的方式对三电极体系外加电压进行电化学反应，其中，电位为-100mV vs RHE，恒电位扫描的时间为100h。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning. The potential was -100 mV vs RHE, and the potentiometric scanning time was 100 h.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2TiC 2纳米片。 (6) Centrifuging the electrolytic solution and washing and drying the solid precipitate to obtain a Mo 2 TiC 2 nanosheet.
实施例3Example 3
(1)将2g的Mo 2TiAlC 2加入到10mL的质量浓度为50％的HF酸溶液中，加热至50℃下反应30h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为7时，对下层固体进行干燥和研磨得到Mo 2TiC 2纳米材料。 (1) 2 g of Mo 2 TiAlC 2 was added to 10 mL of a 50% by mass HF acid solution, and heated to 50 ° C for 30 hours to obtain a reaction solution. After the reaction solution was centrifuged, the lower layer of solid was washed to the supernatant. When the pH value is 7, the underlying solid is dried and ground to obtain a Mo 2 TiC 2 nanomaterial.
(2)取100mg的Mo 2TiC 2纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为异丙醇。 (2) 100 mg of Mo 2 TiC 2 nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was isopropyl alcohol.
(3)将纳米分散液涂覆于碳纸电极上，纳米分散液在碳纸电极上的涂覆量为0.5mg/cm 2。 (3) The nano-dispersion was applied to a carbon paper electrode, and the coating amount of the nano-dispersion on the carbon paper electrode was 0.5 mg/cm 2 .
(4)将上述碳纸电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.05M的H 2SO 4溶液，电解液的pH值为4。 (4) The carbon paper electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system. The electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.05 M, and the pH of the electrolyte is 4.
(5)采用恒电位扫描的方式对三电极体系外加电压进行电化学反应，其中，电位为-500mV vs RHE，恒电位扫描的时间为2h。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning. The potential was -500 mV vs RHE, and the potentiometric scanning time was 2 h.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2TiC 2纳米片。 (6) Centrifuging the electrolytic solution and washing and drying the solid precipitate to obtain a Mo 2 TiC 2 nanosheet.
实施例4Example 4
(1)将2g的Mo 2AlC加入到30mL的质量浓度为30％的HF酸溶液中，加热至45℃下反应48h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行干燥和研磨得到Mo 2C纳米材料。 (1) 2 g of Mo 2 AlC was added to 30 mL of a 30% by mass HF acid solution, heated to 45 ° C for 48 h to obtain a reaction solution, and the reaction liquid was centrifuged to wash the lower layer of the solid to the supernatant. At a pH of 6, the underlying solid is dried and ground to obtain a Mo 2 C nanomaterial.
(2)取60mg的Mo 2C纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为4:1的水和异丙醇的混合液。 (2) 60 mg of Mo 2 C nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and isopropyl alcohol in a volume ratio of 4:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.08mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.08 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.5M的H 2SO 4溶液，电解液的pH值为0。 (4) The glassy carbon electrode, the mercury sulphate electrode and the carbon rod electrode are combined to form a three-electrode system. The electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.5 M, and the pH of the electrolyte is zero.
(5)采用恒电位扫描的方式对三电极体系外加电压进行电化学反应，其中，电位为-450mV vs RHE，恒电位扫描的时间为48h。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning. The potential was -450 mV vs RHE, and the potentiometric scanning time was 48 h.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2C纳米片。 (6) Centrifuging the electrolyte and washing and drying the solid precipitate to obtain a Mo 2 C nanosheet.
实施例5Example 5
(1)将2g的Mo 2TiAlC 2加入到30mL的质量浓度为35％的HF酸溶液中，加热至45℃下反应48h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行干燥得到Mo 2TiC 2纳米材料。 (1) 2 g of Mo 2 TiAlC 2 was added to 30 mL of a 35% by mass HF acid solution, and heated to 45 ° C for 48 h to obtain a reaction solution. The reaction solution was centrifuged and the lower layer of solid was washed until the supernatant was washed. When the pH value is 6, the lower layer solid is dried to obtain a Mo 2 TiC 2 nano material.
(2)取6mg的Mo 2TiC 2纳米材料分散于1mL的分散液中得到纳米分散液，其中分散液为体积比为3:1的水和乙醇的混合液。 (2) 6 mg of Mo 2 TiC 2 nanomaterial was dispersed in 1 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and ethanol in a volume ratio of 3:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.05M的H 2SO 4溶液，电解液的pH值为4。 (4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.05 M, and the pH of the electrolyte is 4.
(5)采用阴极线性扫描的方式对三电极体系外加电压进行电化学反应，其中，电位扫描的范围为0～-400mV vs RHE，电位扫描的速率为5mV/s，电 位扫描的圈数为2000圈。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of cathode linear scanning. The potential scanning range was 0--400 mV vs RHE, the potential scanning rate was 5 mV/s, and the potential scanning circle was 2000. ring.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2TiC 2纳米片。 (6) Centrifuging the electrolytic solution and washing and drying the solid precipitate to obtain a Mo 2 TiC 2 nanosheet.
实施例6Example 6
(1)将1g的Mo 2AlC加入到20mL的质量浓度为40％的HF酸溶液中，加热至45℃下反应40h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行干燥和研磨得到Mo 2C纳米材料。 (1) Add 1 g of Mo 2 AlC to 20 mL of a 40% by mass HF acid solution, heat to 45 ° C for 40 h to obtain a reaction solution, centrifuge the reaction solution, and wash the lower layer of the solid to the supernatant. At a pH of 6, the underlying solid is dried and ground to obtain a Mo 2 C nanomaterial.
(2)取50mg的Mo 2C纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为2:1的水和异丙醇的混合液。 (2) 50 mg of Mo 2 C nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and isopropyl alcohol in a volume ratio of 2:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.1M的H 2SO 4溶液，电解液的pH值为3。 (4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.1 M, and the pH of the electrolyte is 3.
(5)采用阴极线性扫描的方式对三电极体系外加电压进行电化学反应，其中，电位扫描的范围为0～-550mV vs RHE，电位扫描的速率为100mV/s，电位扫描的圈数为2000圈。(5) Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning, wherein the potential scanning range is 0--550 mV vs RHE, the potential scanning rate is 100 mV/s, and the potential scanning circle is 2000. ring.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2C纳米片。 (6) Centrifuging the electrolyte and washing and drying the solid precipitate to obtain a Mo 2 C nanosheet.
实施例7Example 7
(1)将0.5g的Mo 2TiAlC 2加入到30mL的质量浓度为35％的HF酸溶液中，加热至55℃下反应24h得到反应液，将反应液离心后对下层固体进行洗 涤至上层清液的pH值为7时，对下层固体进行干燥和研磨得到Mo 2TiC 2纳米材料。 (1) 0.5 g of Mo 2 TiAlC 2 was added to 30 mL of a 35% by mass HF acid solution, and heated to 55 ° C for 24 hours to obtain a reaction solution. After centrifuging the reaction solution, the lower layer of solid was washed to the supernatant. When the pH of the liquid is 7, the underlying solid is dried and ground to obtain a Mo 2 TiC 2 nanomaterial.
(2)取10mg的Mo 2TiC 2纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为1:1的水和乙醇的混合液。 (2) 10 mg of Mo 2 TiC 2 nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and ethanol in a volume ratio of 1:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为0.01M的H 2SO 4溶液，电解液的pH值为6。 (4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a H 2 SO 4 solution having a molar concentration of 0.01 M, and the pH of the electrolyte is 6.
(5)采用阴极线性扫描的方式对三电极体系外加电压进行电化学反应，其中，电位扫描的范围为0～-500mV vs RHE，电位扫描的速率为50mV/s，电位扫描的圈数为3000圈。(5) Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning, wherein the potential scanning range is 0--500 mV vs RHE, the potential scanning rate is 50 mV/s, and the potential scanning circle is 3000. ring.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2TiC 2纳米片。 (6) Centrifuging the electrolytic solution and washing and drying the solid precipitate to obtain a Mo 2 TiC 2 nanosheet.
实施例8Example 8
(1)将0.5g的Mo 2TiAlC 2加入到30mL的质量浓度为30％的HF酸溶液中，加热至55℃下反应24h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为7时，对下层固体进行干燥和研磨得到Mo 2TiC 2纳米材料。 (1) 0.5 g of Mo 2 TiAlC 2 was added to 30 mL of a 30% by mass HF acid solution, and heated to 55 ° C for 24 hours to obtain a reaction solution. After the reaction solution was centrifuged, the lower layer of solid was washed to the supernatant. When the pH of the liquid is 7, the underlying solid is dried and ground to obtain a Mo 2 TiC 2 nanomaterial.
(2)取10mg的Mo 2TiC 2纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为1:1的水和乙醇的混合液。 (2) 10 mg of Mo 2 TiC 2 nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and ethanol in a volume ratio of 1:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.04mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.04 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为磷酸缓冲溶液，电解液的pH值为7。(4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a phosphate buffer solution, and the pH of the electrolyte is 7.
(5)采用恒电位扫描的方式对三电极体系外加电压进行电化学反应，其中，电位为-100mV vs RHE，恒电位扫描的时间为100h。(5) Electrochemical reaction was carried out on the applied voltage of the three-electrode system by means of potentiostatic scanning. The potential was -100 mV vs RHE, and the potentiometric scanning time was 100 h.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥。(6) Centrifuging the electrolyte and washing and drying the solid precipitate.
结果显示，当调节电解液的pH值为7时，在中性的电解体系下，Mo 2TiC 2纳米材料基本上无法被剥离。 The results show that when the pH of the electrolyte is adjusted to 7, the Mo 2 TiC 2 nanomaterial is substantially not peeled off under a neutral electrolytic system.
实施例9Example 9
(1)将1g的Mo 2AlC加入到20mL的质量浓度为40％的HF酸溶液中，加热至45℃下反应40h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行干燥和研磨得到Mo 2C纳米材料。 (1) Add 1 g of Mo 2 AlC to 20 mL of a 40% by mass HF acid solution, heat to 45 ° C for 40 h to obtain a reaction solution, centrifuge the reaction solution, and wash the lower layer of the solid to the supernatant. At a pH of 6, the underlying solid is dried and ground to obtain a Mo 2 C nanomaterial.
(2)取50mg的Mo 2C纳米材料分散于10mL的分散液中得到纳米分散液，其中分散液为体积比为1:1的水和异丙醇的混合液。 (2) 50 mg of Mo 2 C nanomaterial was dispersed in 10 mL of a dispersion to obtain a nanodispersion, wherein the dispersion was a mixture of water and isopropyl alcohol in a volume ratio of 1:1.
(3)将纳米分散液涂覆于玻碳电极上，纳米分散液在玻碳电极上的涂覆量为0.06mg/cm 2。 (3) The nano-dispersion was applied to a glassy carbon electrode, and the coating amount of the nano-dispersion on the glassy carbon electrode was 0.06 mg/cm 2 .
(4)将上述玻碳电极、硫酸亚汞电极和碳棒电极构成三电极体系，三电极体系的电解液为摩尔浓度为1M的KOH溶液，电解液的pH值为12。(4) The above-mentioned glassy carbon electrode, mercury sulphate electrode and carbon rod electrode constitute a three-electrode system, and the electrolyte of the three-electrode system is a KOH solution having a molar concentration of 1 M, and the pH of the electrolyte is 12.
(5)采用阴极线性扫描的方式对三电极体系外加电压进行电化学反应，其中，电位扫描的范围为0～-550mV vs RHE，电位扫描的速率为100mV/s，电位扫描的圈数为2000圈。(5) Electrochemical reaction of the applied voltage of the three-electrode system by means of cathode linear scanning, wherein the potential scanning range is 0--550 mV vs RHE, the potential scanning rate is 100 mV/s, and the potential scanning circle is 2000. ring.
(6)对电解液进行离心处理并对固体沉淀进行洗涤和干燥得到Mo 2C纳米片。 (6) Centrifuging the electrolyte and washing and drying the solid precipitate to obtain a Mo 2 C nanosheet.
结果显示，当调节电解液的pH值为12时，在碱性的电解体系下，Mo 2TiC 2纳米材料会与碱性溶液发生反应，从而破坏了Mo 2TiC 2纳米材料的片状结构。 The results show that when the pH of the electrolyte is adjusted to 12, the Mo 2 TiC 2 nanomaterial reacts with the alkaline solution under an alkaline electrolysis system, thereby destroying the sheet structure of the Mo 2 TiC 2 nanomaterial.
实施例10Example 10
(1)将0.5g的Mo 2TiAlC 2加入到10mL的质量浓度为50％的HF酸溶液中，加热至35℃下反应48h得到反应液，将反应液离心后对下层固体进行洗涤至上层清液的pH值为6时，对下层固体进行干燥得到Mo 2TiC 2纳米材料。 (1) Add 0.5 g of Mo 2 TiAlC 2 to 10 mL of a 50% by mass HF acid solution, heat to 35 ° C for 48 h to obtain a reaction solution, centrifuge the reaction solution, and wash the lower layer of solid to the supernatant. When the pH of the liquid is 6, the lower solid is dried to obtain a Mo 2 TiC 2 nanomaterial.
(2)将上述得到的Mo 2TiC 2MXene重新分散到10ml水溶液中，再加入1ml质量分数为40％的四丁基氢氧化铵。在氩气保护条件下搅拌1h。之后3500rpm离心1h，收集上清液即为有机溶液剥离得到的Mo 2TiC 2纳米片。 (2) The Mo 2 TiC 2 MXene obtained above was redispersed into 10 ml of an aqueous solution, and 1 ml of tetrabutylammonium hydroxide having a mass fraction of 40% was further added. Stir under argon protection for 1 h. After centrifugation at 3500 rpm for 1 h, the supernatant was collected and the Mo 2 TiC 2 nanosheets obtained by peeling off the organic solution.
对实施例1剥离前、剥离中和剥离后的含Mo的MXene纳米材料进行扫描电镜测试，结果如图3所示。其中，进行扫描电镜测试时采用的是型号为Zeiss Supra 55VP的扫描电镜测试仪进行测试。The MXene nanomaterials containing Mo before, during, and after stripping of Example 1 were subjected to scanning electron microscopy. The results are shown in FIG. Among them, the scanning electron microscope test was carried out by using a scanning electron microscope tester of the type Zeiss Supra 55VP.
对实施例1中制备得到的Mo 2TiC 2纳米材料及Mo 2TiC 2纳米片分别进行扫描透射电镜测试，结果如图5和图6所示。其中，进行扫描透射电镜测试时采用进行扫描电镜测试时采用的是型号为STEM,JEOL JEM-ARM200F的扫描电镜测试仪进行测试。 The Mo 2 TiC 2 nanomaterials prepared in Example 1 and the Mo 2 TiC 2 nanosheets were respectively subjected to scanning transmission electron microscopy, and the results are shown in FIGS. 5 and 6. Among them, the scanning electron microscope test was carried out by using a scanning electron microscope (STEM) model of STEM, JEOL JEM-ARM200F.
从图3可以看出，我们收集了反应过程中Mo 2TiC 2的样品来研究反应过程中其形貌的变化。如图3所示，反应前，可以看出Mo 2TiC 2是比较松散的层状结构，表面也比较平整，反应一段时间后，其表面和边缘都发生了很大的变化，出现了很多的裂缝，表面也发生了卷曲。等扫描结束后，可以看出Mo 2TiC 2层状纳米片形成了。图4为与图3对应的含Mo的MXene纳米材料 剥离过程的示意图，反映了含Mo的MXene纳米材料的剥离过程。 As can be seen from Figure 3, we collected samples of Mo 2 TiC 2 during the reaction to study the change in morphology during the reaction. As shown in Fig. 3, before the reaction, it can be seen that Mo 2 TiC 2 is a relatively loose layered structure, and the surface is relatively flat. After a period of reaction, the surface and edges of the reaction change greatly, and a lot of Cracks and curls on the surface. After the end of the scanning, it can be seen that the Mo 2 TiC 2 layered nanosheets are formed. 4 is a schematic view showing the peeling process of the Mo-containing MXene nanomaterial corresponding to FIG. 3, reflecting the peeling process of the Mo-containing MXene nanomaterial.
图5为实施例1中制备得到的Mo 2TiC 2纳米材料扫描透射电镜照片，从图中可以看出Al原子层在HF处理过程中被移除了，Ti原子层被两层Mo原子层夹在中间。 5 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanomaterial prepared in Example 1. It can be seen from the figure that the Al atom layer is removed during the HF treatment, and the Ti atom layer is sandwiched by two layers of Mo atoms. in the middle.
图6为实施例1中制备得到的Mo 2TiC 2纳米片的扫描透射电镜照片，电催化活化后可以看到Mo 2TiC 2纳米片上出现了原子缺失，也就是Mo空位。 6 is a scanning transmission electron micrograph of the Mo 2 TiC 2 nanosheet prepared in Example 1. After electrocatalytic activation, atomic defects, that is, Mo vacancies, were observed on the Mo 2 TiC 2 nanosheet.
图7为实施例1中Mo 2TiC 2纳米材料在进行恒电位扫描的电化学活性图，在恒电位扫描过程中，可以观察到电流密度在前10小时内急剧增加，后15h慢慢趋于稳定。 7 is an electrochemical activity diagram of the Mo 2 TiC 2 nanomaterial in Example 1 subjected to constant potential scanning. During the potentiostatic scanning process, the current density can be observed to increase sharply in the first 10 hours, and gradually tend to be in the first 15 hours. stable.
图8为实施例5中Mo 2TiC 2纳米材料在进行阴极线性扫描的极化曲线，在循环阴极线性扫描过程中，随着扫描圈数的增加，电流密度也是一直在增加，在1000圈之后趋于稳定。 8 is a polarization curve of a Mo 2 TiC 2 nanomaterial in a cathode linear scan in Example 5. In the cyclic cathode linear scanning process, as the number of scanning turns increases, the current density also increases, after 1000 cycles. becoming steady.
如图8所示，Mo 2TiC 2MXene在扫描过程中，随着扫描圈数的增加，电化学析氢性能逐渐增加，在1000圈的时候达到最大值，之后其催化活性趋于稳定。析氢过程中性能的提高主要来源于Mo 2TiC 2MXene的电化学剥离。在电化学剥离过程中Mo 2TiC 2纳米片暴露了更多的催化活性表面及造成了大量Mo空位的产生。 8, Mo 2 TiC 2 MXene during the scanning process, as the number of turns scanning electrochemical properties of hydrogen is gradually increased, reached a maximum at the time of 1000 cycles, after which the catalytic activity stable. The improvement in performance during hydrogen evolution is mainly due to the electrochemical stripping of Mo 2 TiC 2 MXene. Mo 2 TiC 2 nanosheets exposed more catalytically active surfaces and caused a large amount of Mo vacancies during electrochemical stripping.
图9是实施例10中利用有机溶剂剥离得到的Mo 2TiC 2纳米片的电催化析氢性能。此催化活性相对较低，相对于Mo 2TiC 2MXene和电化学剥离得到的Mo 2TiC 2纳米片。其主要原因是剥离过程中使用的有机溶剂有部分残留在Mo 2TiC 2纳米片的表面，与其表面的基团，例如O-终止位和OH-终止位，之间形成一定的键合作用，阻挡了与溶液中H 3O +的结合，进而降低其催化析氢反应活性。 Fig. 9 is a graph showing the electrocatalytic hydrogen evolution performance of a Mo 2 TiC 2 nanosheet obtained by peeling off with an organic solvent in Example 10. This catalytic activity is relatively low, compared to Mo 2 TiC 2 MXene and electrochemically stripped Mo 2 TiC 2 nanosheets. The main reason is that some of the organic solvent used in the stripping process remains on the surface of the Mo 2 TiC 2 nanosheet, and a certain bond is formed between the surface group, such as the O-termination site and the OH-termination site. The binding to H 3 O + in the solution is blocked, thereby reducing the catalytic hydrogen evolution reaction activity.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (19)

  1. 一种具有Mo空位的MXene纳米片的制备方法，包括步骤：A method for preparing MXene nanosheets with Mo vacancies, comprising the steps of:
    将含Mo的MXene纳米材料分散于分散液中得到纳米分散液；Dispersing the Mo-containing MXene nano material in the dispersion to obtain a nano-dispersion liquid;
    将所述纳米分散液涂覆于工作电极上；Applying the nanodispersion to a working electrode;
    将所述涂覆有纳米分散液的工作电极与参比电极及对电极组成三电极体系，所述三电极体系的电解液的pH值为0～6；及The working electrode coated with the nano-dispersion liquid and the reference electrode and the counter electrode constitute a three-electrode system, and the pH of the electrolyte of the three-electrode system is 0-6;
    对所述三电极体系外加电压进行电化学剥离和活化得到具有Mo空位的MXene纳米片。Electrochemical stripping and activation of the applied voltage of the three-electrode system yielded MXene nanosheets with Mo vacancies.
  2. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述含Mo的MXene纳米材料选自Mo 2TiC 2纳米材料及Mo 2C纳米材料中的一种。 The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the Mo-containing MXene nanomaterial is one selected from the group consisting of Mo 2 TiC 2 nano materials and Mo 2 C nano materials.
  3. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述分散液选自水、异丙醇和乙醇中的至少一种。The method for producing a MXene nanosheet having Mo vacancies according to claim 1, wherein the dispersion is at least one selected from the group consisting of water, isopropyl alcohol, and ethanol.
  4. 根据权利要求3所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述分散液为水和异丙醇的混合液，其中，所述水与所述异丙醇的体积比为1:4～4:1。The method for preparing a MXene nanosheet having Mo vacancies according to claim 3, wherein the dispersion is a mixture of water and isopropyl alcohol, wherein a volume ratio of the water to the isopropyl alcohol It is 1:4 to 4:1.
  5. 根据权利要求3所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述分散液为水和乙醇的混合液，其中，所述水和所述乙醇的体积比为1:4～4:1。The method for preparing a MXene nanosheet having Mo vacancies according to claim 3, wherein the dispersion is a mixture of water and ethanol, wherein a volume ratio of the water to the ethanol is 1:4 ~4:1.
  6. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述含Mo的MXene纳米材料与所述分散液的用量比为1mg/mL～10mg/mL。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the ratio of the Mo-containing MXene nanomaterial to the dispersion is from 1 mg/mL to 10 mg/mL.
  7. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法， 其特征在于，所述将含Mo的MXene纳米材料分散于分散液的步骤中采用超声波分散的方式进行，所述超声波分散的功率为60W～100W，所述超声波分散的时间为30min～90min。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the step of dispersing the Mo-containing MXene nanomaterial in the dispersion is performed by ultrasonic dispersion, the ultrasonic dispersion The power is 60 W to 100 W, and the ultrasonic dispersion time is 30 min to 90 min.
  8. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述工作电极选自玻碳电极及碳纸电极中的一种，所述纳米分散液在所述工作电极上的涂覆量为0.04mg/cm 2～0.5mg/cm 2。 The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the working electrode is selected from one of a glassy carbon electrode and a carbon paper electrode, and the nanodispersion liquid is at the working electrode The coating amount on the coating is from 0.04 mg/cm 2 to 0.5 mg/cm 2 .
  9. 根据权利要求8所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述纳米分散液在所述玻碳电极上的涂覆量为0.04mg/cm 2，所述纳米分散液在所述碳纸电极上的涂覆量为0.5mg/cm 2。 The method for preparing a MXene nanosheet having Mo vacancies according to claim 8, wherein a coating amount of the nanodispersion liquid on the glassy carbon electrode is 0.04 mg/cm 2 , the nanodispersion liquid The coating amount on the carbon paper electrode was 0.5 mg/cm 2 .
  10. 根据权利要求1或8所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述参比电极为硫酸亚汞电极，所述对电极为碳棒电极。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1 or 8, wherein the reference electrode is a mercury sulphate electrode, and the counter electrode is a carbon rod electrode.
  11. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述对所述三电极体系外加电压进行电化学反应得到具有Mo空位的MXene纳米片的步骤中采用恒电位扫描的方式外加电压进行电化学反应，所述恒电位扫描的方式中电位为-100mV vs RHE～-500mV vs RHE，所述采用恒电位扫描的方式外加电压进行电化学反应的时间为2h～100h。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the step of electrochemically reacting the applied voltage of the three-electrode system to obtain a MXene nanosheet having Mo vacancies adopts a constant potential The scanning method is applied with an applied voltage to perform an electrochemical reaction. The potential of the constant potential scanning method is -100 mV vs RHE ～-500 mV vs RHE, and the time for applying the voltage for electrochemical reaction by the method of constant potential scanning is 2 h to 100 h. .
  12. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述对所述三电极体系外加电压进行电化学反应得到具有Mo空位的MXene纳米片的步骤中采用阴极线性扫描的方式外加电压进行电化学反应，所述阴极线性扫描的方式中电位的扫描范围为0～-A mV vs RHE，其中，400≤A≤550；电位扫描的速率为5mV/s～100mV/s，电位扫描的圈数为1000圈～5000圈。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the step of electrochemically reacting the applied voltage of the three-electrode system to obtain a MXene nanosheet having Mo vacancies adopts cathode linearity. The scanning method is applied with an applied voltage to perform an electrochemical reaction. The scanning range of the potential in the linear scanning mode of the cathode is 0 to -A mV vs RHE, wherein 400 ≤ A ≤ 550; the rate of potential scanning is 5 mV/s to 100 mV/ s, the number of turns of the potential scan is 1000 to 5000 circles.
  13. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法， 其特征在于，所述三电极体系的所述电解液选自硫酸、盐酸、磷酸和高氯酸的至少一种。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the electrolyte of the three-electrode system is at least one selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, and perchloric acid.
  14. 根据权利要求13所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述三电极体系的所述电解液的摩尔浓度为0.01M～0.5M。The method for preparing a MXene nanosheet having Mo vacancies according to claim 13, wherein the electrolyte solution has a molar concentration of 0.01 M to 0.5 M.
  15. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述将含Mo的MXene纳米材料分散于分散液中得到纳米分散液的步骤前还包括制备含Mo的MXene纳米材料的步骤：将前驱体MAX加入到HF酸中在35℃～55℃的温度下反应24h～48h得到反应液，将所述反应液离心后对下层固体进行洗涤至上层清液的pH值为6～7。The method for preparing a MXene nanosheet having Mo vacancies according to claim 1, wherein the step of dispersing the Mo-containing MXene nanomaterial in the dispersion to obtain a nano-dispersion further comprises preparing MXene containing Mo The step of the nano material: the precursor MAX is added to the HF acid to react at a temperature of 35 ° C to 55 ° C for 24 h to 48 h to obtain a reaction liquid, and the reaction liquid is centrifuged to wash the lower layer solid to the pH of the supernatant. It is 6 to 7.
  16. 根据权利要求15所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述前驱体MAX选自Mo 2Ga 2C及Mo 2TiAlC 2中的一种。 The method for preparing a MXene nanosheet having Mo vacancies according to claim 15, wherein the precursor MAX is selected from the group consisting of Mo 2 Ga 2 C and Mo 2 TiAlC 2 .
  17. 根据权利要求15所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述HF酸的质量浓度为30％～50％。The method for preparing a MXene nanosheet having Mo vacancies according to claim 15, wherein the HF acid has a mass concentration of 30% to 50%.
  18. 根据权利要求15所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述前驱体MAX与所述HF酸的用量比为0.0167g/mL～0.2g/mL。The method for preparing a MXene nanosheet having Mo vacancies according to claim 15, wherein the ratio of the precursor MAX to the HF acid is 0.0167 g/mL to 0.2 g/mL.
  19. 根据权利要求1所述的具有Mo空位的MXene纳米片的制备方法，其特征在于，所述对所述三电极体系外加电压进行电化学剥离和活化的步骤之后还包括：对所述三电极体系的所述电解液进行抽滤处理得到固体物质，并对所述固体物质进行洗涤和冷冻干燥。The method for preparing an MXene nanosheet having Mo vacancies according to claim 1, wherein the step of electrochemically stripping and activating the applied voltage of the three-electrode system further comprises: treating the three-electrode system The electrolytic solution is subjected to suction filtration to obtain a solid matter, and the solid matter is washed and freeze-dried.
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