CN114351234B - Method for preparing two-dimensional material by electrochemical etching based on coordination chemistry and detection method thereof - Google Patents
Method for preparing two-dimensional material by electrochemical etching based on coordination chemistry and detection method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry and a detection method thereof, 1, the method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has the characteristics of green, safety and high efficiency, and the used reagent is harmless to human bodies and the environment and has obvious etching effect on target materials. 2. The method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has universality in theory, and can finish etching of most materials by selecting a proper complex as an electrolyte active substance on the premise of conforming to objective rules. 3. Compared with the existing electrochemical etching system, the method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has the advantages of clearer mechanism elucidation, great instruction significance for selecting electrolyte, simple operation, easy implementation and high efficiency, and is suitable for large-scale industrial production and application.
Description
Technical field:
the invention relates to the technical field of chemical engineering, in particular to a method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry and a detection method thereof.
The background technology is as follows:
the two-dimensional material has extremely high specific surface area and can provide a plurality of surface active sites, so that the two-dimensional material has extremely wide application prospect in the fields of energy storage, catalysis, photoelectric conversion and the like. The existing effective methods for obtaining the two-dimensional material are mainly divided into a bottom-up method and a top-down method. The former is typically vapor deposition but in very low yields; the latter is typically chemical exfoliation, with high yields but with a high risk of reagents typically used, such as the highly corrosive concentrated sulfuric acid used in Hummer's process for exfoliating graphene, with significant safety implications in experimental operations.
MXene materials are widely used because of their ultrahigh conductivity, abundant and tunable surface functional groups, and strong processability. However, the entire MXene family is mainly obtained by chemically etching the element a in the precursor MAX, and as known, hydrofluoric acid is a chemical substance with strong danger, and long-term use of hydrofluoric acid can cause great harm to human body, and the MBene family also faces the same problems, so that a green, safe and efficient method is urgently needed to obtain the two-dimensional material.
The electrochemical etching method is a method for obtaining a two-dimensional material from top to bottom, and mainly utilizes electrochemical reaction to pump out certain elements in a three-dimensional body phase formed by chemical bonding of two-dimensional forms, so as to obtain the target two-dimensional material. The core of implementing the electrochemical reaction is the design of the electrolytic cell, while the key of the electrolytic cell is the choice of electrolyte. The effective electrolytes commonly used at present are aqueous acidic or alkaline, and have considerable effects, but the electrolytes have certain dangers and no obvious pertinence, so that the reaction lacks accurate purposefulness, and the potential for driving the electrochemical reaction is higher, namely, the potential barrier is very high.
The invention comprises the following steps:
the invention aims to solve the existing problems, and provides a method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry, which is used for overcoming the defects of single electrolyte type and weak purpose in an electrochemical system by selecting a proper ligand as an active substance in electrolyte based on the idea of coordination chemistry and further obtaining a high-quality two-dimensional material by electrochemical etching a three-dimensional precursor formed by chemical bonding of two-dimensional forms.
The technical solution of the invention is as follows:
a method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding active substances into a certain volume of deionized water, stirring with ultrasound under the power of 100W to enable the active substances to be fully dissolved, secondly adding a certain amount of strong electrolyte into the system, stirring until the strong electrolyte is fully dissolved, and obtaining clear and transparent electrolyte, wherein the electrolyte forms a double-electrolyte system, the ionic conductivity is greatly enhanced, and the charge transmission efficiency of the whole circuit is improved;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: mixing the precursor powder and the PVDF aqueous solution in a certain volume of deionized water in a ratio of 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode;
step four: inserting a working electrode, a counter electrode and a reference electrode into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation with the model of CHI760E, wherein the workstation is controlled by a computer, the three-electrode electrochemical etching system is constructed to improve the visualization degree of reaction conditions, the set voltage is constant and controllable relative to the reference electrode, and simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell with the electrolyte on a stirrer with heating, and keeping the rotating speed at 250rpm and the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation, a constant voltage of 0.9V is applied, bubbles can be found to appear on a counter electrode continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on the filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, powder is obtained after drying, and the two-dimensional material is obtained after collection.
Preferably, the active material is a material containing an active ligand having a high stability constant after binding to the target extraction element.
Preferably, the active substance is EDTA-2Na or sodium citrate, and scientific and reasonable selection of the active substance in the electrolyte can reduce the reaction barrier to a certain extent.
Preferably, the strong electrolyte is NaCl particles.
Preferably, the precursors are MAX materials and MAB materials, the MAX materials including but not limited to Ti 3 AlC 2 、Nb 4 AlC 3 、Mo 2 Ga 2 C、Mo 2 TiAlC 2 、Ti 2 AlC or V 2 AlC, the MAB material includes but is not limited to Mo 2 AlB 2 、Cr 2 AlB 2 Or MnAlB 2 。
Preferably, the counter electrode is a graphite rod with high conductivity, and the reference electrode is an Ag/AgCl electrode filled with a 3M KCl solution.
A detection method of a two-dimensional material prepared by electrochemical etching based on coordination chemistry comprises the following steps:
step one: turning on the field emission scanning electron microscope, and preheating for 30min;
step two: adhering conductive adhesive on a sample stage, smearing a precursor and obtained powder on the conductive adhesive by using a cotton swab, blowing off excessive powder by using a gas purifying bottle, placing the sample stage into a vacuum cavity of a field emission scanning electron microscope, vacuumizing for 15min, and then observing the surface morphology of the sample by focusing electron beams.
Step three: and carrying out energy spectrum scanning on the precursor and the two-dimensional material, and obtaining the relative content of each element of the two-dimensional material.
The invention has the beneficial effects that:
1. the method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has the characteristics of green, safety and high efficiency, and the used reagent is harmless to human bodies and the environment and has obvious etching effect on target materials.
2. The method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has universality in theory, and can finish etching of most materials by selecting a proper complex as an electrolyte active substance on the premise of conforming to objective rules.
3. Compared with the existing electrochemical etching system, the method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry has the advantages of clearer mechanism elucidation, great instruction significance for selecting electrolyte, simple operation, easy implementation and high efficiency, and is suitable for large-scale industrial production and application.
Description of the drawings:
FIG. 1 is a schematic diagram of an electrochemical etching apparatus based on coordination chemistry according to the present invention;
FIG. 2 is a schematic diagram of an electrochemical etcher based on coordination chemistry in accordance with embodiment 1 of the present invention;
FIG. 3 is a graph showing cyclic voltammograms in different electrolytes in an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of a precursor and a two-dimensional material in an embodiment of the invention;
FIG. 5 shows the content of each element in the precursor in example 1 of the present invention;
FIG. 6 shows the content of each element in the two-dimensional material prepared in example 1 of the present invention.
In the accompanying drawings: 1. a counter electrode; 2. a working electrode; 3. a reference electrode; 4. an electrolytic cell; 5. an electrochemical workstation; 6. and a computer.
The specific embodiment is as follows:
the following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "or/and" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Ti was dissolved in 0.5mL deionized water 3 AlC 2 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then, a constant voltage of 0.9V is applied to an operation interface of an electrochemical workstation 5 by using an i-t function, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, powder is obtained after drying, and the two-dimensional material is obtained after collection.
The detection method of the two-dimensional material prepared by electrochemical etching based on coordination chemistry comprises the following steps:
step one: turning on the field emission scanning electron microscope, and preheating for 30min;
step two: adhering conductive adhesive on a sample stage, smearing a precursor and obtained powder on the conductive adhesive by using a cotton swab, blowing off excessive powder by using a gas purifying bottle, placing the sample stage into a vacuum cavity of a field emission scanning electron microscope, vacuumizing for 15min, and then observing the surface morphology of the sample by focusing electron beams.
Step three: and carrying out energy spectrum scanning on the precursor and the two-dimensional material, and obtaining the relative content of each element of the two-dimensional material.
In terms of working principle, a certain voltage is applied to the electrolyte solution containing only NaCl, so that the whole system starts to react, and the reaction is essentially the reaction of electrolysis water: 2NaCl+2H 2 O＝Cl 2 +2NaOH+H 2 The cathode obtains H 2 Anode gets Cl 2 . Essentially after the introduction of the precursor, another competing reaction occurs at the anode: m-e=m+ and this reaction is preferred over the obtaining of Cl 2 Is a reaction of (a). The reason for this result is due to the difference in the potentials of the two standard electrodes. The cathode reacts with H in the whole system 2 Reduction of O: 2H (H) 2 O+2e＝2OH - +H 2 This is undoubtedly (since only na+ is available for electrons in the cathode outside the water in the whole system, the electrons of this ion will give the metal Na, which in small amounts will strongly exotherm in water, even explode, which obviously does not occur). While the anode has two possible oxidation reactions: m-e=m+ and 2Cl - -2e＝Cl 2 Species with strong reducibility undergo preferentially oxidation reactions, in which the corresponding pair M+/M and Cl 2 The standard electrode potentials of/Cl-were xV (x < 0) and 1.36V, respectively. Meanwhile, according to the applied analysis of the standard electrode potential of the pair of the redox reaction: the smaller the standard electrode potential, the more reducing the pair of reducing species that the electricity is. Say thatThe reducing property of the Ming M is stronger, and the oxidation reaction of the electron losing of the Ming M occurs preferentially. However, due to the limitation of the cathodic reaction, the system is essentially a reaction for electrolyzing water, and in theory, the reaction can be continuously performed only when the applied voltage reaches 1.23V of the decomposition voltage, in fact, the application of the voltage smaller than 1.23V can drive the continuous reaction to be performed, and the reason that the applied potential is obviously reduced is that the generation of the M-EDTA complex reduces the reaction barrier and pulls the reaction to be performed in the direction of the product. In summary, the expected reaction sequence in the system accords with the change rule of the standard electrode potential, the generation of coordination compounds in the product reduces the reaction barrier, the reaction is promoted, and the final electrochemical etching is performed with high efficiency.
As shown in FIG. 3, which is a curve obtained by cyclic voltammetry scanning of the working electrode 2, it can be seen that a larger current step appears at 0.8V in the electrolytic cell 4 system containing the active material EDTA-2Na, while the step lag and the change amplitude are smaller in the NaCl electrolytic cell 4 system without the active material, which indicates that the addition of the EDTA-2Na active material and the generation of the Al-EDTA complex reduce the reaction barrier to a certain extent; it is evident from fig. 4 that the dense packing of the precursor is destroyed and the interlayer spacing is opened after the electrochemical reaction. In fig. 5 and 6, the Al atom content is reduced by more than 50%, indicating that the target element is successfully extracted and the material is successfully etched. In conclusion, by scientifically selecting a proper active substance, the reaction barrier can be obviously reduced, the reaction is promoted, the green and efficient etching of the target precursor is realized, and the final target material is obtained.
Example 2
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Nb in 0.5mL deionized water 4 AlC 3 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
Example 3
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Mo in 0.5mL deionized water 2 Ga 2 Mixing the powder C and PVDF water solution, wherein the ratio of the powder C to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
Example 4
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Mo in 0.5mL deionized water 2 TiAlC 2 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
Example 5
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Ti was dissolved in 0.5mL deionized water 2 AlC powder and PVDF aqueous solution are mixed, and the ratio of the AlC powder to the PVDF aqueous solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
Example 6
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Mo in 0.5mL deionized water 2 AlB 2 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction was completed, the working electrode 2 was immersed in 50mL of deionized water
In a 100mL beaker, carrying out ultrasonic treatment for 30min under the power of 100W, vacuum filtering liquid, collecting precipitate on a filter membrane, vacuum drying the precipitate at 60 ℃ for 12h, and collecting dry powder to obtain the two-dimensional material.
Example 7
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor Cr is dissolved in 0.5mL deionized water 2 AlB 2 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
Example 8
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
step one: firstly adding 5.4g of EDTA-2Na powder into a certain volume of deionized water, stirring under ultrasonic agitation at 100W power to enable the EDTA-2Na powder to be fully dissolved, then adding water to control the total volume to be 80mL, and secondly adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are fully dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1: 1. ultrasonic cleaning with deionized water for 3h, drying in an oven at 60 ℃ for 6h, and taking out for standby;
step three: precursor MnAlB is treated in 0.5mL deionized water 2 Mixing the powder and PVDF water solution, wherein the ratio of the powder to the PVDF water solution is 9:1, putting 10mg of the total weight into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, and controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode 2;
step four: inserting a working electrode 2, a counter electrode 1 and a reference electrode 3 into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation 5 with the model of CHI760E, controlling the workstation by a computer 6, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell 4 with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at 25 ℃ in a standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to appear on a counter electrode 1 continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode 2 is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on a filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, and the dried powder is collected, so that the two-dimensional material is obtained.
The foregoing is only for the understanding of the method and core idea of the invention, and it should be noted that it will be obvious to those skilled in the art that numerous changes and modifications can be made without departing from the principle of the invention, and these changes and modifications fall within the protection scope of the claims of the invention.
Claims (2)
1. The method for preparing the two-dimensional material by electrochemical etching based on coordination chemistry is characterized by comprising the following steps of:
step one: firstly adding active substances into a certain volume of deionized water, wherein the active substances are substances containing active ligands and having high stability constants after being combined with target extraction elements; the active substance is EDTA-2Na, the active substance is fully dissolved by ultrasonic stirring under the power of 100W, and then a certain amount of strong electrolyte which is NaCl particles is added into the system; stirring until the electrolyte is completely dissolved to obtain clear and transparent electrolyte;
step two: cutting carbon paper into a rectangle of 1cm×5cm as a substrate, and adding acetone: water = 1:1, ultrasonically cleaning the mixed system for 3 hours by deionized water for 3 hours, drying the mixed system in an oven at 60 ℃ for 6 hours, and taking out the mixed system for later use;
step three: mixing the precursor powder and the PVDF aqueous solution in a certain volume of deionized water in a ratio of 9:1, 10mg of total weight, putting the mixture into an ultrasonic instrument, mixing for 1h, dripping the mixed system obtained in the step on the carbon paper obtained in the step two by using a dropper, controlling the coating area to be about 1cm multiplied by 1cm to obtain a working electrode, wherein the precursor is MAX material or MAB material, and the MAX material is Ti 3 AlC 2 、Nb 4 AlC 3 、Mo 2 Ga 2 C、Mo 2 TiAlC 2 、Ti 2 AlC or V 2 AlC, the MAB material is Mo 2 AlB 2 、Cr 2 AlB 2 Or MnAlB 2 ；
Step four: inserting a working electrode, a counter electrode and a reference electrode into the electrolyte obtained in the first step, connecting the three electrodes with an electrochemical workstation with the model of CHI760E, controlling the workstation by a computer, simultaneously, putting a magneton into the electrolyte, placing an electrolytic cell filled with the electrolyte on a stirrer with heating, maintaining the rotating speed at 250rpm, and maintaining the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of a current step is determined, then an i-t function is used at an operation interface of an electrochemical workstation, a constant voltage of 0.9V is applied, bubbles can be found to appear on a counter electrode continuously, the beginning of a reaction process is indicated, and the reaction time is set to be 12 hours;
step five: after the reaction is completed, the working electrode is soaked in a 100mL beaker containing 50mL of deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, sediment on the filter membrane is collected and placed at the temperature of 60 ℃ for vacuum drying for 12h, powder is obtained after drying, and the two-dimensional material is obtained after collection.
2. The method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry according to claim 1, wherein: the counter electrode is a graphite rod with high conductivity, and the reference electrode is an Ag/AgCl electrode filled with 3M KCl solution.
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