CN113249751B - Two-dimensional titanium carbide supported stable two-phase molybdenum diselenide composite material and preparation method and application thereof - Google Patents
Two-dimensional titanium carbide supported stable two-phase molybdenum diselenide composite material and preparation method and application thereof Download PDFInfo
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Abstract
A stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide and a preparation method and application thereof relate to a composite hydrogen evolution catalyst and a preparation method thereof. The invention aims to solve the problems of high cost and poor stability of the existing electrocatalytic hydrogen evolution catalyst. The stable biphase molybdenum diselenide composite material supported by two-dimensional titanium carbide contains N element with the atomic percentage of 0.2-5 percent, and the titanium carbide is used as MoSe 2 The conducting skeletons of the nano sheets form a communicated three-dimensional network structure, moSe 2 The nano-sheets are uniformly grown on the surface of the titanium carbide in situ. The method comprises the following steps: 1. preparation of Na 2 MoO 4 ‑Ti 3 C 2 A solution; 2. preparation of Se-N 2 H 4 A solution; 3. mixing and carrying out hydrothermal reaction. A stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide is used as a catalyst for hydrogen production by water electrolysis. The invention can obtain the stable biphase molybdenum diselenide composite material supported by two-dimensional titanium carbide.
Description
Technical Field
The invention relates to a composite hydrogen evolution catalyst and a preparation method thereof.
Background
In order to solve the energy crisis, people continuously explore and develop novel clean energy. The hydrogen energy has wide development potential and is expected to replace the traditional energy to become an ideal energy carrier in the future. The water electrolysis hydrogen production technology is expected to combine water decomposition with excessive electric power in non-peak periods, endless but intermittent solar energy and wind power generation on the earth, and realizes the large-scale hydrogen production vision. At present, rare noble metal platinum and the like are the most effective hydrogen evolution catalysts at present due to the advantages of small overpotential, small Tafel slope and the like. However, the disadvantages of high cost and low natural reserves of platinum-based noble metals severely limit their widespread use. Therefore, in order to replace noble metal materials, researchers have desired to develop inexpensive non-noble metal catalyst materials with excellent performance.
The transition metal chalcogenide (TMDs) is a two-dimensional layered material, has the advantages of high stability, easy preparation and the like, shows good electrocatalytic activity and has wide application prospect in the field of hydrogen evolution. Molybdenum diselenide (MoSe) 2 ) Is a promising transition metal chalcogenide with higher conductivity than the most typical molybdenum disulfide. However, molybdenum diselenide has the disadvantage of being easy to stack as other two-dimensional nanomaterials. Moreover, the thermodynamically stable 2H phase molybdenum diselenide is a semiconductor, and its conductivity is still relatively weak. Meanwhile, only molybdenum atoms and selenium atoms on the edges of the 2H-phase molybdenum diselenide have electrocatalytic activity, and atoms in the basal plane do not have catalytic activity, so that the application of the molybdenum diselenide in the field of electrocatalytic hydrogen evolution is greatly limited. In contrast, the 1T phase molybdenum diselenide has better conductivity and basal-plane active sites than the H phase molybdenum diselenide. Unfortunately, the 1T phase structure is thermodynamically unstable and can be gradually converted to a 2H structure at room temperature.
The synthesis method of molybdenum diselenide mainly comprises the following steps: mechanical stripping, liquid phase ultrasonic stripping, lithium ion intercalation stripping, chemical vapor deposition and hydrothermal reaction. Wherein the hydrothermal method has the advantages of simple operation, low cost, controllable product appearance, high purity and the like
Disclosure of Invention
The invention aims to solve the problems of high cost and poor stability of the existing electrocatalytic hydrogen evolution catalyst, and provides a stable two-dimensional titanium carbide supported two-phase molybdenum diselenide composite material, and a preparation method and application thereof.
The stable biphase molybdenum diselenide composite material supported by two-dimensional titanium carbide contains N element with the atomic percentage of 0.2-5 percent, and the titanium carbide is used as MoSe 2 The conducting skeletons of the nano sheets form a communicated three-dimensional network structure, moSe 2 The nano-sheets are uniformly grown on the surface of the titanium carbide in situ; the MoSe is 2 The nano sheet is only 1-10 Mo atomic layers thick, the 002 crystal face spacing is 0.65-1.00 nm, and the nano sheet is a 2H and 1T dual-phase coexisting structure.
The preparation method of the stable two-dimensional titanium carbide supported biphase molybdenum diselenide composite material comprises the following steps:
1. mixing Na 2 MoO 4 ·2H 2 Dissolving O in the mixed solution of absolute ethyl alcohol and deionized water, stirring until the solution is clear, and then adding a thin Ti layer 3 C 2 Sonicating to obtain Na 2 MoO 4 -Ti 3 C 2 A solution;
2. adding Se powder to N 2 H 4 ·H 2 Stirring the mixture in O solution at the temperature of between 20 and 80 ℃ until the solution turns deep red to obtain Se-N 2 H 4 A solution;
3. na is mixed with 2 MoO 4 -Ti 3 C 2 Dropwise addition of the solution to Se-N 2 H 4 Obtaining a mixed solution in the solution; transferring the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction to obtain a reaction product; and cleaning the reaction product, and drying to obtain the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide.
A stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide is used as a catalyst for hydrogen production by water electrolysis.
The invention has the beneficial effects that:
1. the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide prepared by the invention has good charge conduction capability; firstly, the two-dimensional layered titanium carbide has good conductivity, and can make up the defect of the conductivity of the molybdenum diselenide as a conductive framework of the molybdenum diselenide, and simultaneously prevent the molybdenum diselenide from being stacked, thereby improving the overall conductivity of the composite material; secondly, the two-dimensional layered titanium carbide and the molybdenum diselenide nanosheets form an interconnected three-dimensional network structure, which is beneficial to the permeation of electrolyte and the rapid conduction of ions/electrons;
2. the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide, which is prepared by the invention, has rich active sites; firstly, the size of the molybdenum diselenide nano-sheet is extremely small, the thickness of the molybdenum diselenide nano-sheet is only 1-10 Mo atomic layers, and more edge active sites can be provided; secondly, molybdenum diselenide nanosheets are uniformly dispersed on the surface of the two-dimensional titanium carbide, no obvious agglomeration phenomenon exists, and more effective active sites are exposed; thirdly, the spacing between crystal faces of the molybdenum diselenide nanosheets (002) is 0.65-1.00 nm, the molybdenum diselenide nanosheets have obvious broadening compared with a standard 2H phase, the crystal structure of the molybdenum diselenide nanosheets is a mixed phase of 1T and 2H, and a large number of basal plane active sites and 1T/2H phase interface active sites are provided. Fourthly, the composite material contains 0.2 to 5at.% of heteroatom N, and abundant additional active sites are introduced;
3. the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide prepared by the invention has high catalytic activity; firstly, molybdenum diselenide is a typical two-dimensional layered material, and shows good electrocatalytic activity due to a special lattice structure, an energy band structure and the like; secondly, the titanium carbide not only serves as a conductive framework of the molybdenum diselenide nanosheet, but also has an obvious catalytic effect on the hydrogen evolution activity of the material, and the catalytic activity of the material can be remarkably improved through the strong electron coupling effect at the position of a molybdenum diselenide/titanium carbide heterogeneous interface;
4. the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide prepared by the invention has good structural stability; firstly, molybdenum diselenide nanosheets grow on the surface of titanium carbide in situ, are tightly and firmly combined with the titanium carbide, and are not easy to fall off in the reaction process; secondly, the heterogeneous interface of the two-dimensional titanium carbide framework and molybdenum diselenide and the 1T/2H phase interface are beneficial to better compatibility of structural stress, so that the stable existence of the 1T phase structure is ensured;
5. the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide, which is prepared by the invention, can optimize the electrochemical performance of a final product by changing the titanium carbide amount, and can accurately optimize the performance by adjusting the number of crystal planes and the interlayer spacing of molybdenum diselenide (002) crystal planes, is favorable for reasonable design and accurate control of the material, and provides theoretical basis and technical support for research and practical application of an electro-catalytic hydrogen evolution catalyst.
6. The stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide, which is prepared by the invention, is applied to the field of electrocatalytic hydrogen evolution and is 10mAcm -2 At a current density of (2), the overpotential in the alkaline solution is only 150mV, and the Tafel slope is 90mV dec -1 After 1000 cycles, the electrochemical performance is almost not attenuatedThe compound shows good cycling stability;
7. the precursor used by the stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide has the advantages of abundant earth reserves, environmental friendliness, low cost, ingenious process, low price of processing equipment, simple procedures and methods, low cost and contribution to large-scale industrial production.
The invention can obtain a stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide.
Drawings
FIG. 1 shows MoSe prepared in example one 2 /Ti 3 C 2 X-ray diffraction spectrum of composite material, in which 1 is MoSe prepared in the first example 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
FIG. 2 shows MoSe prepared in example one 2 /Ti 3 C 2 Raman spectrum of composite material, in which 1 is MoSe prepared in example one 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
FIG. 3 shows MoSe prepared in example one 2 /Ti 3 C 2 Scanning electron microscope images and element distribution images of the composite material;
FIG. 4 shows MoSe prepared in example one 2 /Ti 3 C 2 Transmission electron microscope images of the composite;
FIG. 5 shows MoSe prepared in example one 2 /Ti 3 C 2 XPS spectra of the composite;
FIG. 6 is a polarization diagram, in which 1 is carbon paper and 2 is MoSe prepared according to the first example 2 /Ti 3 C 2 Composite material, 3 is MoSe prepared by comparative example one 2 And 4 is a thin Ti layer prepared in one step of the example 3 C 2 ；
FIG. 7 is a Tafel slope plot, in which FIG. 1 is MoSe prepared according to example one 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
FIG. 8 is an impedance spectrum, in which FIG. 1 is MoSe prepared according to example I 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 3 thin Ti layer prepared in one step of the example 3 C 2 ；
FIG. 9 shows MoSe prepared in example one 2 /Ti 3 C 2 Polarization curves of the composite material before and after 1000 cycles and 2000 cycles, wherein 1 is initial, 2 is 1000 cycles, and 3 is 2000 cycles.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide contains 0.2 to 5 atomic percent of N element, and the titanium carbide is used as MoSe 2 The conducting skeletons of the nano sheets form a communicated three-dimensional network structure, moSe 2 The nano-sheets are uniformly grown on the surface of the titanium carbide in situ; the MoSe is 2 The nano sheet is only 1-10 Mo atomic layers thick, the 002 crystal face spacing is 0.65-1.00 nm, and the nano sheet is a 2H and 1T dual-phase coexisting structure.
The second embodiment is as follows: the embodiment is a preparation method of a stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide, which is completed according to the following steps:
1. mixing Na 2 MoO 4 ·2H 2 Dissolving O in the mixed solution of absolute ethyl alcohol and deionized water, stirring until the solution is clear, and then adding a thin Ti layer 3 C 2 Sonicating to obtain Na 2 MoO 4 -Ti 3 C 2 A solution;
2. adding Se powder to N 2 H 4 ·H 2 Stirring the mixture in O solution at the temperature of between 20 and 80 ℃ until the solution turns deep red to obtain Se-N 2 H 4 A solution;
3. na is mixed with 2 MoO 4 -Ti 3 C 2 Dropwise addition of the solution to Se-N 2 H 4 Obtaining a mixed solution in the solution; transferring the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction to obtain a reaction product; and cleaning the reaction product, and drying to obtain the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: na as described in step one 2 MoO 4 ·2H 2 The volume ratio of the mass of the O to the mixed solution of the absolute ethyl alcohol and the deionized water is (0.1 g-0.2 g) 100mL. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the thin layer Ti described in the step one 3 C 2 The volume ratio of the mass of the (C) to the mixed solution of the absolute ethyl alcohol and the deionized water is (10 mg-500 mg): 200mL.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one is 1; the power of ultrasonic treatment in the step one is 100W-180W, and the time of ultrasonic treatment is 0.2 h-2 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the thin layer Ti described in the step one 3 C 2 The preparation method comprises the following steps:
1. 1.56g LiF is added into 20mL HCl solution with the concentration of 6mol/L, stirred until the solution is clear, and then 1g Ti is added 3 AlC 2 Obtaining a mixed solution; placing the mixed solution into a water bath kettleContinuously stirring for 48h at 38 ℃ to obtain a black reaction product; firstly washing 3 times by using 1mol/L HCl solution, then washing 3 times by using 1mol/L LiCl solution, and finally washing by using deionized water until the pH value of the supernatant is more than 6 to obtain Ti 3 C 2 A suspension; for Ti 3 C 2 Centrifuging the suspension, collecting precipitate, and freeze drying at-80 deg.C for 2 hr to obtain thin Ti layer 3 C 2 . The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: mass and N of Se powder in the second step 2 H 4 ·H 2 The volume ratio of the O solution is (0.07 g-0.08 g) to (7 mL-8 mL); n in the second step 2 H 4 ·H 2 The mass fraction of the O solution is 50-90%. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: na described in step three 2 MoO 4 -Ti 3 C 2 Solution with Se-N 2 H 4 The volume ratio of the solution is (1-20) to (1-10). The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the temperature of the hydrothermal reaction in the third step is 150-240 ℃, and the time of the hydrothermal reaction is 6-15 h; in the third step, deionized water and absolute ethyl alcohol are used for alternately cleaning reaction products; the drying temperature in the third step is 40-80 ℃, and the drying time is 5-20 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the stable two-phase molybdenum diselenide composite material supported by two-dimensional titanium carbide is used as a catalyst for hydrogen production by water electrolysis.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The first embodiment is as follows: stable biphase diselenide supported by two-dimensional titanium carbideMolybdenum composite material (MoSe) 2 /Ti 3 C 2 The preparation method of the composite material) comprises the following steps:
1. preparation of thin layer Ti 3 C 2 ：
1.56g LiF is added into 20mL HCl solution with the concentration of 6mol/L, stirred until the solution is clear, and then 1g Ti is added 3 AlC 2 Obtaining a mixed solution; putting the mixed solution into a water bath kettle, and continuously stirring for 48 hours at 38 ℃ to obtain a black reaction product; firstly, washing for 3 times by using 1mol/L HCl solution, then washing for 3 times by using 1mol/L LiCl solution, and finally washing by using deionized water until the pH value of the supernatant is more than 6 to obtain Ti 3 C 2 A suspension; for Ti 3 C 2 Centrifuging the suspension, collecting precipitate, and freeze drying at-80 deg.C for 2 hr to obtain thin Ti layer 3 C 2 ；
2. Adding 0.141g of Na 2 MoO 4 ·2H 2 Dissolving O in 100mL of mixed solution of absolute ethyl alcohol and deionized water, stirring until the solution is clear, and adding 100mg of thin Ti 3 C 2 Then carrying out ultrasonic treatment for 1h at the ultrasonic treatment power of 150W to obtain Na 2 MoO 4 -Ti 3 C 2 A solution;
the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step two is 1;
3. 0.079g of Se powder was added to 7.5mL of 80 mass percent N 2 H 4 ·H 2 Adding into O solution, stirring at 50 deg.C until the solution turns deep red to obtain Se-N 2 H 4 A solution;
4. mixing Na 2 MoO 4 -Ti 3 C 2 Dropwise addition of the solution to Se-N 2 H 4 Obtaining a mixed solution in the solution; transferring the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction for 10 hours at 200 ℃ to obtain a reaction product; washing the reaction product by using deionized water and absolute ethyl alcohol alternately, and then drying the reaction product in vacuum for 15 hours at the temperature of 60 ℃ to obtain the stable two-phase molybdenum diselenide composite material (MoSe) supported by two-dimensional titanium carbide 2 /Ti 3 C 2 A composite material).
Comparative example one: moSe 2 The preparation method comprises the following steps:
1. adding 0.141g of Na 2 MoO 4 ·2H 2 Dissolving O in 100mL of mixed solution of absolute ethyl alcohol and deionized water, and stirring until the solution is clear to obtain Na 2 MoO 4 A solution;
the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one is 1;
2. 0.079g of Se powder was added to 7.5mL of 80 mass percent N 2 H 4 ·H 2 Adding into O solution, stirring at 50 deg.C until the solution turns deep red to obtain Se-N 2 H 4 A solution;
3. mixing Na 2 MoO 4 Dropwise addition of the solution to Se-N 2 H 4 Obtaining a mixed solution in the solution; transferring the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction for 10 hours at 200 ℃ to obtain a reaction product; washing the reaction product by using deionized water and absolute ethyl alcohol alternately, and then drying for 15 hours in vacuum at 60 ℃ to obtain MoSe 2 。
FIG. 1 shows MoSe prepared in example one 2 /Ti 3 C 2 X-ray diffraction spectrum of composite material, in which 1 is MoSe prepared in the first example 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
By reaction with pure MoSe 2 And Ti 3 C 2 Comparing XRD spectra of the two groups, finding MoSe in figure 1 2 /Ti 3 C 2 The diffraction peaks of the composite material belong to MoSe 2 And Ti 3 C 2 From this, it can be seen that the product synthesized in this example is MoSe 2 /Ti 3 C 2 A composite material.
FIG. 2 shows MoSe prepared in example one 2 /Ti 3 C 2 Raman spectrum of composite material, FIG. 1 shows the first embodimentPrepared MoSe 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
At 237 and 286cm in the figure -1 Two characteristic peaks at (A) respectively correspond to MoSe 2 In plane A of 1g And out-of-plane E1 2g Mode(s). And MoSe 2 Raman spectrum of (1) to MoSe 2 /Ti 3 C 2 A of the composite Material 1g Peak intensity superior to E1 2g Peak intensity of (a). This phenomenon means that Ti 3 C 2 Adding of (2) to MoSe 2 More edge locations are exposed and thus more catalytically active sites are provided.
FIG. 3 shows MoSe prepared in example one 2 /Ti 3 C 2 Scanning electron microscope images and element distribution images of the composite material;
FIGS. 3 (a) and (b) are the MoSe prepared in example one 2 /Ti 3 C 2 Scanning electron microscope images of the composite material at low power; as can be seen from fig. 3 (a) and (b), the synthesized product has a three-dimensional network structure, which is favorable for the penetration of electrolyte and the rapid conduction of ions/electrons; the molybdenum diselenide nanosheet is extremely small in size, and can provide more edge active sites; the molybdenum diselenide nanosheets are uniformly dispersed on the surface of the two-dimensional titanium carbide, obvious agglomeration phenomenon is avoided, and more effective active sites are exposed.
FIG. 3 (c) shows MoSe prepared according to example one 2 /Ti 3 C 2 Distribution images of the elements of the composite material;
as can be seen from FIG. 3 (c), moSe 2 /Ti 3 C 2 The elements in the composite material are uniformly distributed. In addition to Mo, se, ti and C, N was also included, indicating that the compound was successfully doped with N in an amount of 2.4at.%.
FIG. 4 shows MoSe prepared in example one 2 /Ti 3 C 2 Transmission electron microscope images of the composite;
FIG. 4 (a) is MoSe prepared according to example one 2 /Ti 3 C 2 Composite materialThe inset is the corresponding selected area electron diffraction;
as can be seen from FIG. 4 (a), the product synthesized in this example is MoSe 2 /Ti 3 C 2 A composite material.
As can be seen from fig. 4 (b), (c) and (d), the number of layers of the molybdenum diselenide nanosheets synthesized in the present embodiment is 2-8, (002) the interplanar spacing is 0.65nm and 0.97nm, the crystal structure thereof is a mixed phase of 1T and 2H, and a large number of basal plane active sites and 1T/2H phase interface active sites can be provided; the (002) interplanar spacing of the titanium carbide was 1.4nm.
FIG. 5 shows MoSe prepared in example one 2 /Ti 3 C 2 XPS spectra of the composite;
as can be seen from fig. 5, the product synthesized in this example successfully incorporates N element; the strong electron coupling effect exists at the position of the molybdenum diselenide/titanium carbide heterogeneous interface, and the catalytic activity of the material can be obviously improved.
Water electrolysis hydrogen production experiment:
preparing an electrode:
(1) The MoSe prepared in the first example 2 /Ti 3 C 2 Fully grinding the composite material, the carbon nano tube and the PVDF according to a mass ratio of 8; coating the uniformly mixed slurry on carbon paper to be used as a working electrode;
(2) The thin Ti layer prepared in the first step of the example 3 C 2 Fully grinding the carbon nano tube and the PVDF according to a mass ratio of 8; coating the uniformly mixed slurry on carbon paper to be used as a working electrode;
(3) The MoSe prepared in the first comparative example 2 Fully grinding the carbon nano tube and the PVDF according to a mass ratio of 8; coating the uniformly mixed slurry on carbon paper to be used as a working electrode;
electrochemical testing
MoSe from the preparation of example one in a standard three electrode cell 2 /Ti 3 C 2 The composite material is subjected to electrochemical catalytic performance test in 1M KOH electrolyte. All electrochemical tests are typicalMeasurements were performed in a three-electrode system by means of an electrochemical workstation (VMP 3, france). The electrodes prepared from the carbon paper, the (1), (2) and the (3) are respectively used as working electrodes, ag/AgCl is used as a reference electrode, and a carbon rod is used as a counter electrode. The polarization curves of all samples were measured by Linear Sweep Voltammetry (LSV) at a sweep rate of 5mV s -1 . Electrochemical Impedance Spectroscopy (EIS) was studied in the frequency range of 0.1 to 106 HZ.
FIG. 6 is a polarization diagram, in which 1 is carbon paper and 2 is MoSe prepared according to the first example 2 /Ti 3 C 2 Composite material, 3 is MoSe prepared by comparative example one 2 And 4 is a thin Ti layer prepared in one step of the example 3 C 2 ；
As shown in FIG. 6, by comparison, moSe is present 2 /Ti 3 C 2 The hydrogen evolution performance of the composite material is obviously superior to that of pure molybdenum diselenide and titanium carbide, and the catalytic activity of the composite material is the best. At 10mA/cm 2 Under the condition of (1), moSe 2 /Ti 3 C 2 The composite material has an overpotential (150 mV) closest to that of platinum carbon, and the overpotentials of molybdenum diselenide and titanium carbide are 209mV and 239mV, respectively.
FIG. 7 is a Tafel slope plot, in which FIG. 1 is MoSe prepared according to example one 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 3 thin Ti layer prepared in one step of the example 3 C 2 ；
As can be seen from FIG. 7, the MoSe prepared in the first example 2 /Ti 3 C 2 Composite material and MoSe 2 And Ti 3 C 2 Tafel slopes of 90, 120 and 216mV dec, respectively -1 . Example one MoSe preparation 2 /Ti 3 C 2 Tafel slope of the composite is minimal, notes and MoSe 2 And Ti 3 C 2 In contrast, example one prepared MoSe 2 /Ti 3 C 2 The composite material exhibits a faster HER reaction rate, the step determining the reaction rate should be the Heyrovsky reaction, and the reaction follows the Volmer-Heyrovsky mechanism.
FIG. 8 is an impedance spectrum, in which FIG. 1 is MoSe prepared according to example I 2 /Ti 3 C 2 Composite material, 2 is MoSe prepared by comparative example one 2 And 3 is a thin Ti layer prepared by one step of the example 3 C 2 ；
As can be seen from FIG. 8, pure Ti 3 C 2 The charge transfer resistance of (2) was only 0.46 Ω, indicating that titanium carbide had good conductivity. The charge transfer resistance of pure molybdenum diselenide was 14.14 Ω, while the MoSe prepared in example one 2 /Ti 3 C 2 The charge transfer resistance of the composite material is 6.53 omega, which shows that the conductivity of the material is obviously improved after titanium carbide is introduced, and the charge transfer capability is faster. Conductivity is one of the key factors affecting the catalytic performance of a catalyst. Thus, ti 3 C 2 Can improve MoSe 2 Kinetics in the HER process.
FIG. 9 shows MoSe prepared in example one 2 /Ti 3 C 2 Polarization curves before and after the composite material is cycled for 1000 times and 2000 times, wherein 1 is initial, 2 is cycled for 1000 times, and 3 is cycled for 2000 times.
As can be seen from FIG. 9, the MoSe prepared in the first example 2 /Ti 3 C 2 The polarization curve of the composite material after 1000 cycles is completely coincided with that before the cycle, and the polarization curve after 2000 cycles is only slightly attenuated, which shows that the MoSe prepared in the first example 2 /Ti 3 C 2 The composite material has good circulation stability.
Claims (8)
1. A preparation method of a two-dimensional titanium carbide supported stable biphase molybdenum diselenide composite material is characterized in that the two-dimensional titanium carbide supported stable biphase molybdenum diselenide composite material contains N element with the atomic percentage of 0.2-5%, and titanium carbide is used as MoSe 2 The conductive skeletons of the nano sheets form a communicated three-dimensional network structure, moSe 2 The nano-sheets are uniformly grown on the surface of the titanium carbide in situ; the MoSe is 2 The nano sheet is only 1-10 Mo atomic layers thick, the 002 crystal face spacing is 0.65-1.00 nm, and the nano sheet is a 2H and 1T dual-phase coexisting structure; the preparation method comprises the following steps:
1. mixing Na 2 MoO 4 ·2H 2 Dissolving O in the mixed solution of absolute ethyl alcohol and deionized water, stirring until the solution is clear, and then adding a thin Ti layer 3 C 2 Sonicating to obtain Na 2 MoO 4 -Ti 3 C 2 A solution;
2. adding Se powder to N 2 H 4 ·H 2 Stirring the mixture in O solution at the temperature of between 20 and 80 ℃ until the solution turns deep red to obtain Se-N 2 H 4 A solution;
3. na is mixed with 2 MoO 4 -Ti 3 C 2 Dropwise addition of the solution to Se-N 2 H 4 Obtaining a mixed solution in the solution; transferring the mixed solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction to obtain a reaction product; and cleaning the reaction product, and drying to obtain the stable two-phase molybdenum diselenide composite material supported by the two-dimensional titanium carbide.
2. The method of claim 1, wherein the Na is present in step one 2 MoO 4 ·2H 2 The volume ratio of the mass of the O to the mixed solution of the absolute ethyl alcohol and the deionized water is (0.1 g-0.2 g) 100mL.
3. The method of claim 1 or 2, wherein the thin Ti layer is formed in step one 3 C 2 The volume ratio of the mass of the (C) to the mixed solution of the absolute ethyl alcohol and the deionized water is (10 mg-500 mg): 200mL.
4. The method for preparing a two-dimensional titanium carbide-supported stable biphasic molybdenum diselenide composite material according to claim 1 or 2, wherein the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution of the absolute ethyl alcohol and the deionized water in the step one is 1; the power of ultrasonic treatment in the step one is 100W-180W, and the time of ultrasonic treatment is 0.2 h-2 h.
5. The method of claim 4, wherein the thin Ti layer is formed in step one 3 C 2 The preparation method comprises the following steps:
1. 1.56g LiF is added into 20mL HCl solution with the concentration of 6mol/L, stirred until the solution is clear, and then 1g Ti is added 3 AlC 2 Obtaining a mixed solution; putting the mixed solution into a water bath kettle, and continuously stirring for 48 hours at 38 ℃ to obtain a black reaction product; firstly washing 3 times by using 1mol/L HCl solution, then washing 3 times by using 1mol/L LiCl solution, and finally washing by using deionized water until the pH value of the supernatant is more than 6 to obtain Ti 3 C 2 A suspension; for Ti 3 C 2 Centrifuging the suspension, collecting precipitate, and freeze drying at-80 deg.C for 2 hr to obtain thin Ti layer 3 C 2 。
6. The method of claim 5, wherein the Se powder in step two has a mass and a mass of N 2 H 4 ·H 2 The volume ratio of the O solution is (0.07 g-0.08 g) to (7 mL-8 mL); n in the second step 2 H 4 ·H 2 The mass fraction of the O solution is 50-90%.
7. The preparation method of the two-dimensional titanium carbide supported stable biphasic molybdenum diselenide composite material according to claim 6, characterized in that Na is described in step three 2 MoO 4 -Ti 3 C 2 Solution with Se-N 2 H 4 The volume ratio of the solution is (1-20) to (1-10).
8. The preparation method of the two-dimensional titanium carbide supported stable biphase molybdenum diselenide composite material according to claim 7, characterized in that the temperature of the hydrothermal reaction in the third step is 150-240 ℃, and the time of the hydrothermal reaction is 6-15 h; in the third step, deionized water and absolute ethyl alcohol are used for alternately cleaning reaction products; the drying temperature in the third step is 40-80 ℃, and the drying time is 5-20 h.
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