CN109402662B - Preparation method of molybdenum selenide two-dimensional layered titanium carbide composite material - Google Patents

Preparation method of molybdenum selenide two-dimensional layered titanium carbide composite material Download PDF

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CN109402662B
CN109402662B CN201811533250.6A CN201811533250A CN109402662B CN 109402662 B CN109402662 B CN 109402662B CN 201811533250 A CN201811533250 A CN 201811533250A CN 109402662 B CN109402662 B CN 109402662B
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mixed solution
mxene
precipitate
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mixing
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CN109402662A (en
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郑晓航
杨雅倩
苗灵芬
李新忠
隋解和
蔡伟
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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

Abstract

A preparation method of molybdenum selenide two-dimensional layered titanium carbide composite material relates to the preparation of a metal carbide/sulfide composite material. The invention aims to solve the problems of poor conductivity and low ion mobility of the existing molybdenum selenide. The method comprises the following steps: firstly, mixing and stirring Se powder and hydrazine hydrate to obtain selenium-hydrazine hydrate dispersion liquid; MXene-Ti3C2Mixing the dispersion liquid with cetyl trimethyl ammonium bromide, and adding sodium molybdate to obtain cetyl trimethyl ammonium bromide solution; thirdly, mixing the selenium-hydrazine hydrate dispersion liquid and a cetyl trimethyl ammonium bromide solution for reaction to obtain a mixed solution; fourthly, cleaning the mixed solution by deionized water and ethanol, centrifuging and drying in vacuum to obtain MoSe2@MXene‑Ti3C2A composite material. The method is used for preparing the molybdenum selenide two-dimensional layered titanium carbide composite material.

Description

Preparation method of molybdenum selenide two-dimensional layered titanium carbide composite material
Technical Field
The invention relates to a preparation method of a metal carbide/sulfide composite material.
Background
The two-dimensional transition metal carbide (Mxene) has a unique layered structure, excellent conductivity, high electrochemical activity and large specific surface area, and has great application potential in the fields of electrocatalysis and energy storage.
Molybdenum selenide as one of the chalcogenides of transition metals is bonded from layer to layer by weak van der waals forces, and thusCan be exfoliated into two-dimensional graphene-like structures, resulting in unique electronic properties that are different from bulk materials. The exposed active sites at the edges of the membrane render it electrocatalytically active. And the interlayer spacing is larger, and some ions are easily inserted between the molybdenum selenide layers, so that the energy storage effect is good. But the intrinsic conductivity of the material is poor, the ion mobility is low, the rate performance is poor, and the application of the material in the field of energy storage is limited; also because the conductivity is poor and the reaction potential barrier is increased, the prior art regulates and controls the defects of the molybdenum selenide, and the hydrogen evolution property of the molybdenum selenide is that the current density is 10mA/cm2The overpotential is 305mV, thus limiting its application in the fields of catalysis and energy storage.
Disclosure of Invention
The invention provides a preparation method of a molybdenum selenide two-dimensional layered titanium carbide composite material, aiming at solving the problems of poor conductivity and low ion mobility of the existing molybdenum selenide.
The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material comprises the following steps:
firstly, mixing and stirring Se powder and 97-98% of hydrazine hydrate by mass for 12-24 h to obtain selenium-hydrazine hydrate dispersion liquid;
the volume ratio of the Se powder to the hydrazine hydrate with the mass percent of 97-98 percent is (0.8-1.3) mmol:5 mL;
II, mixing MXene-Ti3C2Mixing the dispersion liquid with cetyl trimethyl ammonium bromide, stirring for 0.5-2 h at the temperature of 30-50 ℃, adding sodium molybdate, and stirring for 0.2-2 h to obtain a cetyl trimethyl ammonium bromide solution;
the MXene-Ti3C2The mass ratio of the volume of the dispersion liquid to the cetyl trimethyl ammonium bromide is (10-50) mL:1 g; the MXene-Ti3C2The molar ratio of the volume of the dispersion liquid to the sodium molybdate is (10-15) mL:1 mmol;
the MXene-Ti3C2①, mixing lithium fluoride with hydrochloric acid with a concentration of 8.5-9.5 mol/L, and stirring for 25-35 min to obtain a mixtureSolution A;
the volume ratio of the mass of the lithium fluoride to the hydrochloric acid with the concentration of 8.5-9.5 mol/L is 1g (30-50) mL;
②, mixing MAX-Ti at a speed of 1mL/s to 3mL/s3AlC2Adding the mixture into the mixed solution A, and stirring the mixture for 20 to 24 hours at the temperature of between 35 and 45 ℃ to obtain reaction liquid;
the MAX-Ti3AlC2The mass ratio of the (A) to the mixed solution A is 1g (10-20) mL;
③, centrifuging the reaction solution for 8-12 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant after centrifugation to obtain a precipitate;
④, adding deionized water into the precipitate, mixing uniformly to obtain a precipitate, carrying out ultrasonic treatment on the precipitate for 10-20 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 5-15 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant to obtain the precipitate after primary washing;
the volume ratio of the mass of the precipitate to the volume of the deionized water is 1g (30-40) mL;
⑤, repeating the precipitate after the primary washing according to the step ④ until the pH value of the supernatant is 4-5 to obtain the washed precipitate;
⑥, adding ethanol into the washed precipitate to obtain a mixed solution B, carrying out ultrasonic treatment on the mixed solution B for 0.8 to 1.2 hours under the condition that the ultrasonic power is 700 to 800W, and then centrifuging the mixed solution B for 10 to 15 minutes under the condition that the rotating speed is 8000 to 10000rpm to obtain a lower-layer precipitate washed by the ethanol;
the volume percentage of the washed precipitate in the mixed solution B is 5-10%;
⑦, adding deionized water into the lower-layer sediment washed by the ethanol, mixing uniformly to obtain a mixed solution C, carrying out ultrasonic treatment on the mixed solution C for 20-30 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 2-4 min under the condition that the rotating speed is 3000-4000 rpm, taking the black rice dumpling color supernatant, and drying to obtain MXene-Ti3C2Mixing MXene-Ti3C2The mixture is mixed with water to be mixed,obtaining MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion liquid is 10 mg/mL-15 mg/mL;
the volume percentage of the lower-layer precipitate after ethanol cleaning in the mixed solution C is 2-2.5%;
thirdly, mixing the selenium-hydrazine hydrate dispersion liquid with a cetyl trimethyl ammonium bromide solution, magnetically stirring, and reacting for 8-16 h at the reaction temperature of 160-200 ℃ to obtain a mixed solution D;
the volume ratio of the selenium-hydrazine hydrate dispersion liquid to the cetyl trimethyl ammonium bromide solution is (1.6-2.2): 1;
fourthly, cleaning the mixed solution D by deionized water and ethanol, centrifuging, and finally drying for 1-5 h in vacuum at the temperature of 30-50 ℃ to obtain MoSe2@MXene-Ti3C2The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material is completed.
The invention has the beneficial effects that:
MoSe prepared by the invention2@MXene-Ti3C2The composite material has good performance of preparing hydrogen by electrocatalytic hydrolysis, and the current density is 10mA/cm2Then, MoSe2Overpotential is 360mV, while MoSe2@MXene-Ti3C2The overpotential of the hydrogen evolution reaction is 260mV, and the addition of MXene obviously reduces the overpotential of the hydrogen evolution reaction, because the intrinsic conductivity of the material is improved through the MXene phase, a large amount of electrons can be transmitted in the reaction process, and the prepared composite material has a spherical micro-nano structure, large specific surface area, a large number of active sites and high load capacity, so that the catalytic performance can be effectively improved.
MoSe prepared by the invention2@MXene-Ti3C2The composite material has good lithium (sodium) battery performance that MXene-Ti3C2The high conductivity and the unique microsphere structure shorten the ion migration path and improve the ion mobility, thereby improving the multiplying power performance.
The invention utilizes a hydrothermal method to synthesize MXene-Ti in one step3C2/MoSe2The composite material has the advantages of simple preparation method, low cost, easy regulation and control, convenient industrial production and wide application prospect in the fields of hydrogen production by water electrolysis, energy storage electrodes and the like.
Drawings
FIG. 1 shows MoSe prepared in example one2@MXene-Ti3C2Transmission electron micrographs of the composite;
FIG. 2 shows MoSe2@MXene-Ti3C2And MoSe2Linear scan curve of (1) MoSe2And 2 is MoSe prepared in example one2@MXene-Ti3C2A composite material.
Detailed Description
The first embodiment is as follows: the preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material provided by the embodiment is carried out according to the following steps:
firstly, mixing and stirring Se powder and 97-98% of hydrazine hydrate by mass for 12-24 h to obtain selenium-hydrazine hydrate dispersion liquid;
the volume ratio of the Se powder to the hydrazine hydrate with the mass percent of 97-98 percent is (0.8-1.3) mmol:5 mL;
II, mixing MXene-Ti3C2Mixing the dispersion liquid with cetyl trimethyl ammonium bromide, stirring for 0.5-2 h at the temperature of 30-50 ℃, adding sodium molybdate, and stirring for 0.2-2 h to obtain a cetyl trimethyl ammonium bromide solution;
the MXene-Ti3C2The mass ratio of the volume of the dispersion liquid to the cetyl trimethyl ammonium bromide is (10-50) mL:1 g; the MXene-Ti3C2The molar ratio of the volume of the dispersion liquid to the sodium molybdate is (10-15) mL:1 mmol;
the MXene-Ti3C2①, mixing lithium fluoride and hydrochloric acid with the concentration of 8.5-9.5 mol/L and stirring for 25-35 min to obtain a mixed solution A;
the volume ratio of the mass of the lithium fluoride to the hydrochloric acid with the concentration of 8.5-9.5 mol/L is 1g (30-50) mL;
②, mixing MAX-Ti at a speed of 1mL/s to 3mL/s3AlC2Adding the mixture into the mixed solution A, and stirring the mixture for 20 to 24 hours at the temperature of between 35 and 45 ℃ to obtain reaction liquid;
the MAX-Ti3AlC2The mass ratio of the (A) to the mixed solution A is 1g (10-20) mL;
③, centrifuging the reaction solution for 8-12 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant after centrifugation to obtain a precipitate;
④, adding deionized water into the precipitate, mixing uniformly to obtain a precipitate, carrying out ultrasonic treatment on the precipitate for 10-20 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 5-15 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant to obtain the precipitate after primary washing;
the volume ratio of the mass of the precipitate to the volume of the deionized water is 1g (30-40) mL;
⑤, repeating the precipitate after the primary washing according to the step ④ until the pH value of the supernatant is 4-5 to obtain the washed precipitate;
⑥, adding ethanol into the washed precipitate to obtain a mixed solution B, carrying out ultrasonic treatment on the mixed solution B for 0.8 to 1.2 hours under the condition that the ultrasonic power is 700 to 800W, and then centrifuging the mixed solution B for 10 to 15 minutes under the condition that the rotating speed is 8000 to 10000rpm to obtain a lower-layer precipitate washed by the ethanol;
the volume percentage of the washed precipitate in the mixed solution B is 5-10%;
⑦, adding deionized water into the lower-layer sediment washed by the ethanol, mixing uniformly to obtain a mixed solution C, carrying out ultrasonic treatment on the mixed solution C for 20-30 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 2-4 min under the condition that the rotating speed is 3000-4000 rpm, taking the black rice dumpling color supernatant, and drying to obtain MXene-Ti3C2Mixing MXene-Ti3C2Mixing with water to obtain MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion liquid is 10 mg/mL-15 mg/mL;
the volume percentage of the lower-layer precipitate after ethanol cleaning in the mixed solution C is 2-2.5%;
thirdly, mixing the selenium-hydrazine hydrate dispersion liquid with a cetyl trimethyl ammonium bromide solution, magnetically stirring, and reacting for 8-16 h at the reaction temperature of 160-200 ℃ to obtain a mixed solution D;
the volume ratio of the selenium-hydrazine hydrate dispersion liquid to the cetyl trimethyl ammonium bromide solution is (1.6-2.2): 1;
fourthly, cleaning the mixed solution D by deionized water and ethanol, centrifuging, and finally drying for 1-5 h in vacuum at the temperature of 30-50 ℃ to obtain MoSe2@MXene-Ti3C2The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material is completed.
The beneficial effects of the embodiment are as follows:
MoSe prepared by the present embodiment2@MXene-Ti3C2The composite material has good performance of preparing hydrogen by electrocatalytic hydrolysis, and the current density is 10mA/cm2Then, MoSe2Overpotential is 360mV, while MoSe2@MXene-Ti3C2The overpotential of the hydrogen evolution reaction is 260mV, and the addition of MXene obviously reduces the overpotential of the hydrogen evolution reaction, because the intrinsic conductivity of the material is improved through the MXene phase, a large amount of electrons can be transmitted in the reaction process, and the prepared composite material has a spherical micro-nano structure, large specific surface area, a large number of active sites and high load capacity, so that the catalytic performance can be effectively improved.
MoSe prepared by the present embodiment2@MXene-Ti3C2The composite material has good lithium (sodium) battery performance that MXene-Ti3C2The high conductivity and the unique microsphere structure shorten the ion migration path and improve the ion mobility, thereby improving the multiplying power performance.
The specific embodiment utilizes a hydrothermal method to synthesize MXene-Ti in one step3C2/MoSe2The composite material has simple preparation method, low cost and easy preparationThe method is easy to regulate and control, is convenient for industrial production, and has wide application prospect in the fields of hydrogen production by water electrolysis, energy storage electrodes and the like.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the volume ratio of the Se powder in the step one to the hydrazine hydrate with the mass percent of 97-98 percent is (0.8-1) mmol:5 mL. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: MXene-Ti as described in step two3C2The mass ratio of the volume of the dispersion liquid to the cetyl trimethyl ammonium bromide is (10-40) mL:1 g; MXene-Ti as described in step two3C2The molar ratio of the volume of the dispersion liquid to the sodium molybdate is (10-12) mL:1 mmol. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step two, MXene-Ti3C2And mixing the dispersion liquid with cetyl trimethyl ammonium bromide, stirring for 1-2 h at the temperature of 30-45 ℃, adding sodium molybdate, and stirring for 1-2 h to obtain a cetyl trimethyl ammonium bromide solution. The others are the same as the first to third embodiments.
Fifth embodiment is different from the first to fourth embodiments in that lithium fluoride and hydrochloric acid with a concentration of 8.5mol/L to 9mol/L are mixed and stirred for 25min to 30min in step two ① to obtain a mixed solution A, the volume ratio of the mass of the lithium fluoride to the hydrochloric acid with a concentration of 8.5mol/L to 9mol/L is 1g (30 to 40) mL, and the other embodiments are the same as the first to fourth embodiments.
Sixth embodiment different from the first to fifth embodiments in that MAX-Ti is added at a rate of 1mL/s to 2mL/s in the second step ②3AlC2Adding the mixture into the mixed solution A, and stirring for 22-24 h at the temperature of 35-40 ℃ to obtain a reaction solution; the MAX-Ti3AlC2The mass ratio of (1 g) to the volume of the mixed solution A is 1g (15-20) mL. The rest is the same as the first to the fifth embodiments。
The seventh specific embodiment is different from the first to sixth specific embodiments in that deionized water is added into the precipitate in the second ④, the mixture is uniformly mixed to obtain a precipitate, the precipitate is subjected to ultrasonic treatment for 15min to 20min under the condition that the ultrasonic power is 750W to 800W, then the precipitate is subjected to centrifugation for 5min to 10min under the condition that the rotation speed is 3500rpm to 4000rpm, and the supernatant is removed to obtain a precipitate after primary washing, wherein the volume ratio of the mass of the precipitate to the volume of the deionized water is 1g (35 to 40) mL, and the rest is the same as the first to sixth specific embodiments.
Eighth specific embodiment, the difference between the first specific embodiment and the seventh specific embodiment is that ethanol is added into the washed precipitate in the second step ⑥ to obtain a mixed solution B, the mixed solution B is subjected to ultrasonic treatment for 1 to 1.2 hours under the condition that the ultrasonic power is 750 to 800W, and then the mixed solution B is subjected to centrifugation for 12 to 15 minutes under the condition that the rotation speed is 9000 to 10000rpm to obtain a lower-layer precipitate after the ethanol washing, wherein the volume percentage of the washed precipitate in the mixed solution B is 5 to 8 percent, and the other steps are the same as those in the first to seventh specific embodiments.
The ninth embodiment is different from the first to eighth embodiments in that deionized water is added to the lower-layer precipitate cleaned by ethanol in the second ⑦, the mixture is uniformly mixed to obtain a mixed solution C, the mixed solution C is subjected to ultrasonic treatment for 25 to 30min under the condition that the ultrasonic power is 750 to 800W, then the mixed solution C is subjected to centrifugal treatment for 2 to 3min under the condition that the rotating speed is 3500 to 4000rpm, and black rice dumpling color supernatant is taken to be dried to obtain MXene-Ti3C2Mixing MXene-Ti3C2Mixing with water to obtain MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion is 10 mg/mL-14 mg/mL. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: step three, mixing the selenium-hydrazine hydrate dispersion liquid and a cetyl trimethyl ammonium bromide solution, magnetically stirring, and reacting for 8-12 hours at the reaction temperature of 180-200 ℃ to obtain a mixed solution D; the volume ratio of the selenium-hydrazine hydrate dispersion liquid to the cetyl trimethyl ammonium bromide solution is (1.6-2): 1. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material comprises the following steps:
firstly, mixing and stirring 2mmol of Se powder and 10mL of 98% hydrazine hydrate by mass percent for 20 hours to obtain selenium-hydrazine hydrate dispersion liquid;
secondly, mixing 10mL MXene-Ti3C2Mixing the dispersion with 0.33g of hexadecyl trimethyl ammonium bromide, stirring for 1h at the temperature of 45 ℃, adding 1mmol of sodium molybdate, and stirring for 1h to obtain a hexadecyl trimethyl ammonium bromide solution;
the MXene-Ti3C2①, mixing 1g of lithium fluoride with 40mL of hydrochloric acid with the concentration of 9mol/L, and stirring for 30min to obtain a mixed solution A;
②, 2g of MAX-Ti at a rate of 1mL/s3AlC2Adding the mixture into 40mL of mixed solution A, and stirring for 24h at the temperature of 40 ℃ to obtain a reaction solution;
③, centrifuging the reaction solution for 10min at the rotation speed of 3500rpm, and removing the supernatant to obtain precipitate;
④, adding deionized water into the precipitate, mixing uniformly to obtain a precipitate solution, carrying out ultrasonic treatment on the precipitate solution for 15min under the condition that the ultrasonic power is 750W, then centrifuging for 10min under the condition that the rotating speed is 3500rpm, and removing the supernatant to obtain a precipitate after primary washing;
the volume ratio of the mass of the precipitate to the deionized water is 1g:40 mL;
⑤, repeating the step ④ on the once washed precipitate until the pH of the supernatant is 5 to obtain the washed precipitate;
⑥, adding ethanol into the washed precipitate to obtain a mixed solution B, carrying out ultrasonic treatment on the mixed solution B for 1h under the condition that the ultrasonic power is 750W, and then centrifuging the mixed solution B for 15min under the condition that the rotating speed is 10000rpm to obtain a lower-layer precipitate washed by the ethanol;
the volume percentage of the washed precipitate in the mixed solution B is 8 percent;
⑦, adding deionized water into the lower-layer precipitate cleaned by ethanol, mixing uniformly to obtain a mixed solution C, carrying out ultrasonic treatment on the mixed solution C for 30min under the condition that the ultrasonic power is 750W, centrifuging for 2min under the condition that the rotating speed is 3500rpm, taking the black rice dumpling color supernatant, and drying to obtain MXene-Ti3C2Mixing MXene-Ti3C2Mixing with water to obtain MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion is 14 mg/mL;
the volume percentage of the lower-layer precipitate after ethanol cleaning in the mixed solution C is 2%;
mixing 20mL of selenium-hydrazine hydrate dispersion liquid and 10mL of hexadecyl trimethyl ammonium bromide solution, magnetically stirring, and reacting for 12 hours at the reaction temperature of 200 ℃ to obtain a mixed solution D;
fourthly, cleaning the mixed solution D by deionized water and ethanol, centrifuging, and finally drying for 4 hours in vacuum at the temperature of 50 ℃ to obtain MoSe2@MXene-Ti3C2The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material is completed.
MoSe prepared in this example2@MXene-Ti3C2And carrying out morphology characterization and electrochemical performance test on the composite material.
FIG. 1 shows MoSe prepared in example one2@MXene-Ti3C2Transmission electron micrograph of the composite, from which it can be seen that MoSe was prepared in this example2@MXene-Ti3C2The composite material has a spherical micro-nano structure, the diameter of a large sphere is 800nm, and MoSe is present2The nano-particles are distributed on the surface of the micro-nano sphere, have higher specific surface area and can effectively increase active sites and load capacity.
FIG. 2 shows MoSe2@MXene-Ti3C2And MoSe2Linear scan curve of (1) MoSe2And 2 is MoSe prepared in example one2@MXene-Ti3C2A composite material; tested in an alkaline electrolyte, the electrolyte is a 1mol/LKOH solution, and the current density is 10mA/cm2Then, MoSe2Overpotential is 360mV, while MoSe2@MXene-Ti3C2The overpotential of (a) is 260mV and the addition of MXene significantly reduces the overpotential of the hydrogen evolution reaction.

Claims (10)

1. A preparation method of a molybdenum selenide two-dimensional layered titanium carbide composite material is characterized in that the preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material is carried out according to the following steps:
firstly, mixing and stirring Se powder and 97-98% of hydrazine hydrate by mass for 12-24 h to obtain selenium-hydrazine hydrate dispersion liquid;
the volume ratio of the Se powder to the hydrazine hydrate with the mass percent of 97-98 percent is (0.8-1.3) mmol:5 mL;
II, mixing MXene-Ti3C2Mixing the dispersion liquid with cetyl trimethyl ammonium bromide, stirring for 0.5-2 h at the temperature of 30-50 ℃, adding sodium molybdate, and stirring for 0.2-2 h to obtain a cetyl trimethyl ammonium bromide solution;
the MXene-Ti3C2The mass ratio of the volume of the dispersion liquid to the cetyl trimethyl ammonium bromide is (10-50) mL:1 g; the MXene-Ti3C2The molar ratio of the volume of the dispersion liquid to the sodium molybdate is (10-15) mL:1 mmol;
the MXene-Ti3C2①, mixing lithium fluoride and hydrochloric acid with the concentration of 8.5-9.5 mol/L and stirring for 25-35 min to obtain a mixed solution A;
the volume ratio of the mass of the lithium fluoride to the hydrochloric acid with the concentration of 8.5-9.5 mol/L is 1g (30-50) mL;
②, mixing MAX-Ti at a speed of 1mL/s to 3mL/s3AlC2Adding into the mixed solution A at the temperature of 35-45 DEG CStirring for 20-24 h under the condition to obtain reaction liquid;
the MAX-Ti3AlC2The mass ratio of the (A) to the mixed solution A is 1g (10-20) mL;
③, centrifuging the reaction solution for 8-12 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant after centrifugation to obtain a precipitate;
④, adding deionized water into the precipitate, mixing uniformly to obtain a precipitate, carrying out ultrasonic treatment on the precipitate for 10-20 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 5-15 min under the condition that the rotating speed is 3000-4000 rpm, and removing the supernatant to obtain the precipitate after primary washing;
the volume ratio of the mass of the precipitate to the volume of the deionized water is 1g (30-40) mL;
⑤, repeating the precipitate after the primary washing according to the step ④ until the pH value of the supernatant is 4-5 to obtain the washed precipitate;
⑥, adding ethanol into the washed precipitate to obtain a mixed solution B, carrying out ultrasonic treatment on the mixed solution B for 0.8 to 1.2 hours under the condition that the ultrasonic power is 700 to 800W, and then centrifuging the mixed solution B for 10 to 15 minutes under the condition that the rotating speed is 8000 to 10000rpm to obtain a lower-layer precipitate washed by the ethanol;
the volume percentage of the washed precipitate in the mixed solution B is 5-10%;
⑦, adding deionized water into the lower-layer sediment washed by the ethanol, mixing uniformly to obtain a mixed solution C, carrying out ultrasonic treatment on the mixed solution C for 20-30 min under the condition that the ultrasonic power is 700-800W, then centrifuging for 2-4 min under the condition that the rotating speed is 3000-4000 rpm, taking the black rice dumpling color supernatant, and drying to obtain MXene-Ti3C2Mixing MXene-Ti3C2Mixing with water to obtain MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion liquid is 10 mg/mL-15 mg/mL;
the volume percentage of the lower-layer precipitate after ethanol cleaning in the mixed solution C is 2-2.5%;
thirdly, mixing the selenium-hydrazine hydrate dispersion liquid with a cetyl trimethyl ammonium bromide solution, magnetically stirring, and reacting for 8-16 h at the reaction temperature of 160-200 ℃ to obtain a mixed solution D;
the volume ratio of the selenium-hydrazine hydrate dispersion liquid to the cetyl trimethyl ammonium bromide solution is (1.6-2.2): 1;
fourthly, cleaning the mixed solution D by deionized water and ethanol, centrifuging, and finally drying for 1-5 h in vacuum at the temperature of 30-50 ℃ to obtain MoSe2@MXene-Ti3C2The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material is completed.
2. The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material as claimed in claim 1, wherein the volume ratio of the Se powder to the hydrazine hydrate with the mass percent of 97-98% in the step one is (0.8-1) mmol:5 mL.
3. The method for preparing molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein MXene-Ti in the second step3C2The mass ratio of the volume of the dispersion liquid to the cetyl trimethyl ammonium bromide is (10-40) mL:1 g; MXene-Ti as described in step two3C2The molar ratio of the volume of the dispersion liquid to the sodium molybdate is (10-12) mL:1 mmol.
4. The method for preparing molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein MXene-Ti is added in the second step3C2And mixing the dispersion liquid with cetyl trimethyl ammonium bromide, stirring for 1-2 h at the temperature of 30-45 ℃, adding sodium molybdate, and stirring for 1-2 h to obtain a cetyl trimethyl ammonium bromide solution.
5. The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein in step two ①, lithium fluoride and hydrochloric acid with the concentration of 8.5-9 mol/L are mixed and stirred for 25-30 min to obtain a mixed solution A, and the volume ratio of the mass of the lithium fluoride to the hydrochloric acid with the concentration of 8.5-9 mol/L is 1g (30-40) mL.
6. The method for preparing the molybdenum selenide two-dimensional layered titanium carbide composite material as claimed in claim 1, wherein in the second step ②, MAX-Ti is added at a speed of 1mL/s to 2mL/s3AlC2Adding the mixture into the mixed solution A, and stirring for 22-24 h at the temperature of 35-40 ℃ to obtain a reaction solution; the MAX-Ti3AlC2The mass ratio of (1 g) to the volume of the mixed solution A is 1g (15-20) mL.
7. The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein deionized water is added into the precipitate in the second step ④, the mixture is uniformly mixed to obtain a precipitation solution, the precipitation solution is subjected to ultrasonic treatment for 15min to 20min under the condition that the ultrasonic power is 750W to 800W, then the precipitation solution is subjected to centrifugal treatment for 5min to 10min under the condition that the rotating speed is 3500rpm to 4000rpm, and a supernatant is removed to obtain a precipitate after primary washing, wherein the volume ratio of the mass of the precipitate to the volume of the deionized water is 1g (35-40) mL.
8. The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein ethanol is added to the washed precipitate in the second step ⑥ to obtain a mixed solution B, the mixed solution B is subjected to ultrasonic treatment for 1-1.2 h under the condition that the ultrasonic power is 750-800W, and then the mixed solution B is subjected to centrifugal treatment for 12-15 min under the condition that the rotating speed is 9000-10000 rpm to obtain an ethanol-washed lower-layer precipitate, wherein the volume percentage of the washed precipitate in the mixed solution B is 5-8%.
9. The method for preparing a molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein the deionized water is added to the lower-layer precipitate washed with ethanol in the second ⑦ step, and the mixture is uniformly mixed to obtain a mixtureThe solution C is subjected to ultrasonic treatment for 25-30 min under the condition that the ultrasonic power is 750-800W, then the mixed solution C is centrifuged for 2-3 min under the condition that the rotating speed is 3500-4000 rpm, and the black rice dumpling color supernatant is dried to obtain MXene-Ti3C2Mixing MXene-Ti3C2Mixing with water to obtain MXene-Ti3C2A dispersion liquid; the MXene-Ti3C2The concentration of the dispersion is 10 mg/mL-14 mg/mL.
10. The preparation method of the molybdenum selenide two-dimensional layered titanium carbide composite material according to claim 1, wherein the third step is to mix the dispersion of selenium-hydrazine hydrate and the solution of cetyl trimethyl ammonium bromide and magnetically stir, and then react for 8 to 12 hours at the reaction temperature of 180 to 200 ℃ to obtain a mixed solution D; the volume ratio of the selenium-hydrazine hydrate dispersion liquid to the cetyl trimethyl ammonium bromide solution is (1.6-2): 1.
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