CN114351234A - 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 provided by the invention has the characteristics of greenness, safety and high efficiency, and used reagents are harmless to human bodies and environment and have obvious etching effect on target materials. 2. The method for preparing the two-dimensional material by the electrochemical etching based on the coordination chemistry has universality theoretically, and can finish the 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 the electrochemical etching based on coordination chemistry has the advantages of clearer mechanism explanation, great guiding significance for selecting the electrolyte, simplicity and convenience in operation, easiness in implementation and high efficiency, and is suitable for large-scale industrial production and application.
Description
The technical field is as follows:
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.
Background art:
the two-dimensional material has extremely high specific surface area and can provide a plurality of surface active sites, so the two-dimensional material has extremely wide application prospect in the fields of energy storage, catalysis, photoelectric conversion and the like. Currently, effective methods for obtaining two-dimensional materials are mainly divided into bottom-up and top-down methods. The former is typically vapor deposited but with low yield; the latter method is typically chemical stripping, and although the yield is high, the reagents used are generally at a high risk, such as concentrated sulfuric acid with strong corrosivity used in Hummer's method for stripping graphene, which has a significant safety hazard in experimental operations.
MXene materials are widely used due to their advantages of ultra-high conductivity, abundant and tunable surface functional groups, and strong processability. However, at present, the whole MXene family is obtained by mainly using hydrofluoric acid to chemically etch the element A in the precursor MAX of the MXene family, as is well known, hydrofluoric acid is a chemical substance with high risk, which causes great harm to human bodies after long-term use, and 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 is mainly characterized in that a certain element in a three-dimensional bulk phase formed by two-dimensional form through chemical bonding is extracted by using an electrochemical reaction, so that a target two-dimensional material is obtained. The core of performing the electrochemical reaction is the design of the electrolytic cell, and the key to the electrolytic cell is the choice of the electrolyte. At present, the commonly used effective electrolytes are acidic or alkaline in water systems and have considerable effects, but the electrolytes have certain dangerousness and no obvious pertinence, so that the reaction lacks accurate purposiveness, and the potential for driving the electrochemical reaction is higher, namely the potential has a high energy barrier.
The invention content is as follows:
the invention aims to solve the existing problems, and provides a method for preparing a high-quality two-dimensional material by electrochemical etching based on coordination chemistry, which is used for overcoming the defects of single electrolyte type and weak pertinence in an electrochemical system.
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:
the method comprises the following steps: firstly, adding active substances into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the active substances, secondly, adding a certain amount of strong electrolyte into the system, and stirring until the strong electrolyte is completely dissolved to obtain a clear and transparent electrolyte, wherein the ionic conductivity of the electrolyte forming a double electrolyte system is greatly enhanced, and the charge transmission efficiency of the whole circuit is improved;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: mixing the precursor powder and the PVDF aqueous solution in a certain volume of deionized water, wherein the ratio of the precursor powder to the PVDF aqueous solution is 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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, controlling the workstation by a computer, improving the visualization degree of reaction conditions by constructing a three-electrode electrochemical etching system, and setting the voltage to be constant and controllable relative to the reference electrode, meanwhile, putting magnetons into the electrolyte, placing an electrolytic cell filled with the electrolyte on a stirrer with a heater, keeping the rotating speed at 250rpm, and keeping the temperature at the standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation, a constant voltage of 0.9V is applied, bubbles can be found to continuously appear on a counter electrode, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: after the reaction is finished, the working electrode is soaked in a 100mL beaker filled with 50mL deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, precipitate 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 the powder is collected.
Preferably, the active substance is an active ligand-containing substance having a high stability constant after binding to the target abstracting 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, and the MAX materials include but are not limited to Ti3AlC2、Nb4AlC3、Mo2Ga2C、Mo2TiAlC2、Ti2AlC or V2AlC, the MAB material including but not limited to Mo2AlB2、Cr2AlB2Or MnAlB2。
Preferably, the counter electrode is a highly conductive graphite rod 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:
the method comprises the following steps: opening a field emission scanning electron microscope, and preheating for 30 min;
step two: adhering conductive adhesive on a sample table, smearing the precursor and the obtained powder on the conductive adhesive by using a cotton swab, blowing off redundant powder by using a gas purification bottle, placing the sample table into a vacuum cavity of a field emission scanning electron microscope, vacuumizing for 15min, and then observing the surface appearance of the sample by focusing an electron beam.
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 greenness, safety and high efficiency, and the used reagent is harmless to human bodies and the environment and has an obvious etching effect on target materials.
2. The method for preparing the two-dimensional material by the electrochemical etching based on the coordination chemistry has universality theoretically, and can finish the 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 the electrochemical etching based on coordination chemistry has the advantages of clearer mechanism explanation, great guiding significance for selecting the electrolyte, simplicity and convenience in operation, easiness in 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 the principle of an electrochemical etching machine based on coordination chemistry in embodiment 1 of the present invention;
FIG. 3 is a plot of cyclic voltammograms in different electrolytes in accordance with an embodiment of the present invention;
FIG. 4 is a scanning electron microscope image of a precursor and a two-dimensional material according to an embodiment of the invention;
FIG. 5 shows the contents of elements in the precursor of example 1;
FIG. 6 shows the contents of the respective elements in the two-dimensional material prepared in example 1 of the present invention.
In the drawings: 1. a counter electrode; 2. a working electrode; 3. a reference electrode; 4. an electrolytic cell; 5. an electrochemical workstation; 6. a computer.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "or/and" 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:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Ti in 0.5mL deionized water3AlC2Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 0.9V is applied, bubbles can be found on a counter electrode 1 to appear continuously, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: after the reaction is finished, the working electrode 2 is soaked in a 100mL beaker filled with 50mL deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, precipitate 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 the powder is collected.
The detection method of the two-dimensional material prepared by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: opening a field emission scanning electron microscope, and preheating for 30 min;
step two: adhering conductive adhesive on a sample table, smearing the precursor and the obtained powder on the conductive adhesive by using a cotton swab, blowing off redundant powder by using a gas purification bottle, placing the sample table into a vacuum cavity of a field emission scanning electron microscope, vacuumizing for 15min, and then observing the surface appearance of the sample by focusing an electron beam.
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 an electrolyte solution only containing NaCl, so that the whole system starts to react, and the reaction is essentially the reaction of electrolyzed water: 2NaCl +2H2O＝Cl2+2NaOH+H2Cathodic obtaining H2Anodic formation of Cl2. Substantially after the introduction of the precursor, another reaction occurs at the anodeWar reaction: m-e ═ M +, and this reaction gives preference to Cl2The reaction of (1). This result occurs because of the difference in the potentials of the two standard electrodes. In the whole system, the reaction at the cathode is H2Reduction reaction of O: 2H2O+2e＝2OH-+H2This goes without saying (since the only thing that the cathode can get electrons is Na + in addition to water in the whole system, the electrons of this ion get metallic Na, which is strongly exothermic in water even in small amounts, even explosions, which obviously does not occur). While there are two possible oxidation reactions that can occur at the anode: m-e ═ M + and 2Cl--2e＝Cl2The strongly reducing species preferentially undergo oxidation reactions in which the corresponding pairs of electrons M +/M and Cl occur2The standard electrode potentials of the/Cl-are xV (x < 0) and 1.36V, respectively. Meanwhile, according to the application analysis of the standard electrode potential of the couple in which the redox reaction occurs: the lower the standard electrode potential, the more reductive the reductive species in the couple is demonstrated. This indicates that M is more reductive and oxidation reaction with electron loss occurs preferentially. However, due to the limitation of cathode reaction, the system is also the reaction of electrolytic water essentially, theoretically, the applied voltage can be continued until the applied voltage reaches the decomposition voltage of 1.23V, and actually, the applied voltage of less than 1.23V can drive the reaction to be continued, so that the reason that the applied potential is obviously reduced is that the reaction barrier is reduced due to the generation of M-EDTA complex, and the reaction is pulled to the direction of the product. In conclusion, the expected successive occurrence of the reactions in the system conforms to the change rule of the standard electrode potential, and the generation of the coordination compound in the product reduces the reaction potential barrier, promotes the reaction to proceed, and finally the electrochemical etching occurs efficiently.
As shown in fig. 3, a curve obtained by cyclic voltammetry scanning of the working electrode 2 can be seen that a large current step appears at 0.8V in the electrolytic cell 4 system containing the active substance EDTA-2Na, while a step lag and a small change amplitude occur in the NaCl electrolytic cell 4 system containing no active substance, which indicates that the reaction barrier is reduced to a certain extent by adding the EDTA-2Na active substance and generating the Al-EDTA complex; it is apparent from fig. 4 that the dense packing of the precursor is broken and the interlayer spacing is opened after the electrochemical reaction. In fig. 5 and 6, the Al atomic content is suddenly 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 to be carried out, 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:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Nb in 0.5mL deionized water4AlC3Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the precipitate, and thus obtaining the two-dimensional material.
Example 3
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Mo in 0.5mL deionized water2Ga2Mixing the powder C and the PVDF aqueous solution, wherein the ratio of the powder C to the PVDF aqueous solution is 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL of deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the filter membrane, and thus obtaining the two-dimensional material.
Example 4
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Mo in 0.5mL deionized water2TiAlC2Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL of deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the filter membrane, and thus obtaining the two-dimensional material.
Example 5
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Ti in 0.5mL deionized water2Mixing AlC powder and PVDF aqueous solution, wherein the ratio of the AlC powder to the PVDF aqueous solution is 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL of deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the filter membrane, and thus obtaining the two-dimensional material.
Example 6
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Mo in 0.5mL deionized water2AlB2Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: after the reaction is completed, the working electrode 2 is soaked in 50mL of deionized water
And (3) carrying out ultrasonic treatment for 30min in a 100mL beaker under the power of 100W, carrying out vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting the dried powder, and obtaining 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:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor Cr is added into 0.5mL deionized water2AlB2Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the precipitate, and thus obtaining the two-dimensional material.
Example 8
A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry comprises the following steps:
the method comprises the following steps: firstly, adding 5.4g of EDTA-2Na powder into deionized water with a certain volume, carrying out ultrasonic stirring under the power of 100W to fully dissolve the EDTA-2Na powder, then adding water to control the total volume to be 80mL, secondly, adding a certain amount of 4.6g of NaCl particles into the system, and stirring until the NaCl particles are completely dissolved to obtain a clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: precursor MnAlB is added into 0.5mL deionized water2Mixing the powder with the PVDF aqueous solution in a ratio of 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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 number of CHI760E, controlling the workstation by a computer 6, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell 4 filled with the electrolyte on a stirrer with heating, keeping the rotating speed at 250rpm, and keeping the temperature at a standard state temperature of 25 ℃; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation 5, a constant voltage of 1V is applied, bubbles can be found to continuously appear on a counter electrode 1, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: and after the reaction is finished, soaking the working electrode 2 in a 100mL beaker filled with 50mL deionized water, performing ultrasonic treatment for 30min under the power of 100W, performing vacuum filtration on the liquid, collecting the precipitate on the filter membrane, placing the filter membrane at 60 ℃ for vacuum drying for 12h, collecting, drying and powdering the precipitate, and thus obtaining the two-dimensional material.
The foregoing is only for the purpose of understanding the method and the core concept of the present invention, and it should be noted that modifications and variations can be made by those skilled in the art without departing from the principle of the present invention, and these modifications and variations also fall into the protection scope of the appended claims.
Claims (7)
1. A method for preparing a two-dimensional material by electrochemical etching based on coordination chemistry is characterized by comprising the following steps:
the method comprises the following steps: firstly, adding active substances into deionized water with a certain volume, carrying out ultrasonic stirring under 100W power to fully dissolve the active substances, secondly, adding a certain amount of strong electrolyte into the system, and stirring until the strong electrolyte is completely dissolved to obtain clear and transparent electrolyte;
step two: carbon paper was cut into a rectangle of 1cm × 5cm as a base, and acetone: water 1: 1 for 3 hours, then ultrasonically cleaning the mixture for 3 hours by using deionized water, drying the mixture for 6 hours in an oven at the temperature of 60 ℃, and taking the mixture out for later use;
step three: mixing the precursor powder and the PVDF aqueous solution in a certain volume of deionized water, wherein the ratio of the precursor powder to the PVDF aqueous solution is 9: 1, putting the mixture with the total weight of 10mg into an ultrasonic instrument, mixing for 1h, dripping the mixed system 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, controlling the workstation by a computer, simultaneously putting magnetons into the electrolyte, placing an electrolytic cell filled with the electrolyte on a stirrer with a heater, keeping the rotating speed at 250rpm, and keeping the temperature at 25 ℃ of the standard state; firstly, cyclic voltammetry scanning is carried out, the voltage range of current step is determined, then an i-t function is used on an operation interface of an electrochemical workstation, a constant voltage of 0.9V is applied, bubbles can be found to continuously appear on a counter electrode, the reaction process is indicated to start, and the reaction time is set to be 12 h;
step five: after the reaction is finished, the working electrode is soaked in a 100mL beaker filled with 50mL deionized water, ultrasonic treatment is carried out for 30min under the power of 100W, liquid is filtered in vacuum, precipitate 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 the powder is collected.
2. The method for preparing two-dimensional material by electrochemical etching based on coordination chemistry according to claim 1, wherein the electrochemical etching comprises the following steps: the active substance is a substance containing an active ligand with a high stability constant after being combined with a target dissociating element.
3. The method for preparing two-dimensional material by electrochemical etching based on coordination chemistry according to claim 2, wherein: the active substance is EDTA-2Na or sodium citrate.
4. The method for preparing two-dimensional material by electrochemical etching based on coordination chemistry according to claim 1, wherein the electrochemical etching comprises the following steps: the strong electrolyte is NaCl particles.
5. The method for preparing two-dimensional material by electrochemical etching based on coordination chemistry according to claim 1, wherein the electrochemical etching comprises the following steps: the precursors are MAX materials and MAB materials, and the MAX materials include but are not limited to Ti3AlC2、Nb4AlC3、Mo2Ga2C、Mo2TiAlC2、Ti2AlC or V2AlC, the MAB material including but not limited to Mo2AlB2、Cr2AlB2Or MnAlB2。
6. The method for preparing two-dimensional material by electrochemical etching based on coordination chemistry according to claim 1, wherein the electrochemical etching comprises the following steps: the counter electrode is a graphite rod with high conductivity, and the reference electrode is an Ag/AgCl electrode filled with 3M KCl solution.
7. A method for the detection of two-dimensional materials prepared by electrochemical etching based on coordination chemistry according to any one of claims 1 to 6, comprising the following steps:
the method comprises the following steps: opening a field emission scanning electron microscope, and preheating for 30 min;
step two: adhering conductive adhesive on a sample table, smearing the precursor and the obtained powder on the conductive adhesive by using a cotton swab, blowing off redundant powder by using a gas purification bottle, placing the sample table into a vacuum cavity of a field emission scanning electron microscope, vacuumizing for 15min, and then observing the surface appearance of the sample by focusing an electron beam.
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.
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