CN111514909B - Two-dimensional material VSe with different defect degrees 2 Preparation method of (1) - Google Patents
Two-dimensional material VSe with different defect degrees 2 Preparation method of (1) Download PDFInfo
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- 230000007547 defect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title description 10
- 239000010453 quartz Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 33
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 18
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- 239000010411 electrocatalyst Substances 0.000 abstract description 6
- WCQOLGZNMNEYDX-UHFFFAOYSA-N bis(selanylidene)vanadium Chemical compound [Se]=[V]=[Se] WCQOLGZNMNEYDX-UHFFFAOYSA-N 0.000 description 48
- 239000011669 selenium Substances 0.000 description 34
- 239000013078 crystal Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
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- 239000010410 layer Substances 0.000 description 6
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- 229910052723 transition metal Inorganic materials 0.000 description 5
- -1 transition metal chalcogenide Chemical class 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
Two-dimensional material VSe with different defect degrees 2 Belonging to the technical field of new material and clean energy for electrocatalytic hydrogen production. Firstly, weighing vanadium powder and selenium powder as raw materials, mixing and grinding the raw materials, and transferring the raw materials into a quartz tube, wherein the molar ratio of the vanadium powder to the selenium powder is 1: (1.6-2.0); then vacuumizing the quartz tube and sealing the quartz tube; and finally, vertically putting the sealed vacuum quartz tube into a vertical furnace, heating to 700-900 ℃ in an air atmosphere, and preserving heat for 24-72 hours at 700-900 ℃. The invention sets the mol ratio of the vanadium powder to the selenium powder as 1: (1.6-2.0), and the molar ratio of the vanadium powder to the selenium powder is regulated and controlled in the range to obtain VSe with different defect degrees 2 A two-dimensional material. VSe 2 When the two-dimensional material is applied to an electrocatalyst, more active sites can be exposed due to the defects, so that the catalytic activity of the two-dimensional material in the catalytic hydrogen evolution process is greatly improved.
Description
Technical Field
The invention belongs to the technical field of new materials and clean energy for electrocatalytic hydrogen production, and particularly relates to VSe with different defect degrees 2 Two-dimensional materials and their use as electrocatalysts with high hydrogen evolution activity.
Background
The hydrogen energy is expected to become one of important clean energy in future life due to the advantages of zero pollution, zero emission, high heat value and the like. Among the methods for obtaining hydrogen energy, the hydrogen is produced by electrolyzing water, because the raw material water is convenient to obtain, and the hydrogen can generate water after being combusted, the hydrogen can be recycled, so that the electrolyzed water is expected to become a main mode for obtaining the hydrogen energy. Therefore, the search for a catalytic material for use in electrolysis of water has been the subject of intense research in recent years.
The two-dimensional transition metal chalcogenide (TMDs) can provide more electron transmission channels and rich active sites for charge storage, is considered as a first-choice electrode material of batteries and capacitors, plays an important role in fuel cells, metal-air batteries and hydrogen preparation as a catalyst, and has important significance for replacing noble metals such as platinum and the like to become a new-generation efficient and green catalyst. The method for preparing the transition metal sulfide mainly comprises the following steps: solid phase methods, lift-off methods, chemical Vapor Deposition (CVD), hydrothermal methods, and solvothermal methods. Vanadium diselenide (VSe) 2 ) The two-dimensional transition metal chalcogenide compound is a typical two-dimensional transition metal chalcogenide compound, the structure of which comprises three atomic layers, a V atomic layer is embedded between two Se atomic layers, the two Se atomic layers are similar to a sandwich structure and exist in a unit form of Se-V-Se, two Se atoms are tightly combined with the V atom in a covalent bond mode, and weak van der Waals force exists between the layers. The invention patent CN201811176598.4 adopts a hydrothermal method to prepare VSe 2 The nanosheet and the patent CN201710563798.4 adopt the chemical vapor deposition method to prepare the two-dimensional VSe 2 A film. However, vanadium diselenide (VSe) is currently available 2 ) During the preparation process, the selenium precursor will usually be the raw materialAnd the excessive amount is that the molar ratio of the selenium precursor to the vanadium precursor is more than 2, so that the sandwich structure is reserved and a large-area single crystal film is synthesized.
Disclosure of Invention
The invention provides a two-dimensional material VSe with different defect degrees 2 When the two-dimensional material obtained by the preparation method is used as an electrocatalyst, the catalytic activity of hydrogen evolution of electrolyzed water can be effectively improved.
The technical scheme adopted by the invention is as follows:
two-dimensional material VSe with different defect degrees 2 The method for producing (1), characterized by comprising the steps of;
Further, the oxygen/acetylene flame in step 2 is generated by mixed ignition of acetylene and oxygen, wherein the molar ratio of acetylene to oxygen is 1:3.
Further, the invention provides a two-dimensional material VSe with different defect degrees 2 The preparation method comprises the following steps that the molar ratio of vanadium powder to selenium powder is 1: (1.6-2.0) changing the molar ratio of vanadium powder and selenium powder, and adjusting and controlling the obtained two-dimensional material VSe 2 The degree of defect of (a).
The invention also provides the two-dimensional material VSe with different defect degrees 2 Application in electrocatalytic hydrogen production.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a two-dimensional material VSe with different defect degrees 2 The preparation method comprises the following steps of setting the molar ratio of the raw materials of vanadium powder to selenium powder as 1: (1.6-2.0), and VSe with different defect degrees can be obtained by regulating the molar ratio of vanadium powder to selenium powder in the range 2 A two-dimensional material. VSe 2 When the two-dimensional material is applied to an electrocatalyst, more active sites can be exposed due to the defects, so that the catalytic activity of the two-dimensional material in the catalytic hydrogen evolution process is greatly improved, and a novel two-dimensional material with adjustable hydrogen evolution catalytic activity is obtained.
Drawings
FIG. 1 is a diagram showing a real object of a vacuum quartz tube filled with a sample obtained in step 2 of example 1 of the present invention;
FIG. 2 is the VSe obtained in example 2 1.8 SEM images of the samples;
FIG. 3 is VSe from example 2 1.8 A TEM image of the sample;
FIG. 4 is VSe obtained in example 3 2.0 SEM images of the samples at different magnifications; wherein (a) and (b) represent different magnifications;
FIG. 5 is an XRD pattern of the samples obtained in examples 1 to 3;
FIG. 6 is a polarization curve obtained at a scan rate of 5mV/s for three samples, carbon Cloth (CC), and commercial 20% Pt/C catalyst obtained in examples 1-3;
FIG. 7 is a Tafel slope for the polarization curves obtained for the three samples obtained in examples 1-3 and the commercial 20% Pt/C catalyst at a scan rate of 5 mV/s.
Detailed Description
The technical scheme of the invention is further detailed in the following by combining the drawings and specific examples:
the invention aims to provide a novel two-dimensional material-VSe with different defect degrees 2 The electrocatalyst is prepared from high-purity vanadium powder and high-purity selenium powder as vanadium source and selenium source by controlling the molar ratio of vanadium powder to selenium powder to obtain VSe with different defect degrees 2 Sample and then making it into working electrodeThe device is applied to electrocatalytic hydrogen production, and the catalytic device also comprises a reference electrode and a counter electrode.
Example 1
Two-dimensional material VSe with different defect degrees 2 The preparation method specifically comprises the following steps;
Example 2
Two-dimensional material VSe with different defect degrees 2 The preparation method specifically comprises the following steps;
FIG. 2 is the VSe obtained in example 2 1.8 SEM image of sample, FIG. 3 is VSe obtained in example 2 1.8 TEM images of the samples. As can be seen from FIGS. 2 and 3, the sample is a small-area bulk structure, because the existence of Se vacancy defects destroys the local periodic arrangement of the crystal lattice, so that the crystal cannot grow in a large area, while the monolayer VSe 2 The small-area blocks are obtained by layer-by-layer overlapping through van der waals force connection.
Example 3
Two-dimensional material VSe with different defect degrees 2 The preparation method of (1), specifically comprising the following steps;
FIG. 4 is VSe obtained in example 3 2.0 SEM images of the samples; it can be seen from the figure that the sample is a sheet-like structure and has a large area, indicating thatWhen the Se vacancy defect is not introduced, the periodic arrangement of crystal lattices cannot be influenced, and the large-area growth of crystals is facilitated.
FIG. 5 is an XRD pattern of samples obtained in examples 1 to 3; as can be seen from the figure, the diffraction peaks of the three samples obtained in examples 1 to 3 can be consistent and corresponding to the characteristic peak of the standard vertebra card JCPDS No.89-1641 without obvious mixed peaks, which indicates that the three samples only have VSe 2 A substance is provided. For VSe 1.6 The sample, which has a broad diffraction peak and poor crystallinity, is mainly due to the presence of a large number of Se vacancy defects that disrupt the lattice periodicity. For VSe 1.8 The sample has a sharp diffraction peak and good crystallinity, and shows that the existence of a small amount of Se vacancy defects does not greatly damage the periodicity of the crystal lattice. VSe 1.6 And VSe 1.8 A common feature of both samples is that they have relatively weak (00 l) diffraction peaks, indicating a short lattice period along the c-direction, which is also a typical spectral feature of transition metal chalcogenide (TMDs) materials. Interestingly, VSe 2.0 Relative intensities of peaks in XRD pattern of sample and VSe 1.8 And VSe 1.6 The relative intensities of the samples are completely different, wherein the intensities of the (00 l) peaks such as (001), (002), (003), (004) and the like show obviously enhanced values, and other peaks are inhibited, and good single crystal characteristics are shown, so that perfect VSe can be prepared without introducing Se vacancy defects 2 And (3) single crystal. Therefore, the molar ratio of the V powder to the Se powder can be regulated to regulate the concentration of Se vacancy defects, so that VSe can be regulated 2 The crystallinity of (2).
And (3) testing the electrocatalytic performance:
grinding the sample obtained in the embodiment 1-3 and the conductive carbon black according to the mass ratio of 8:2 for 1 hour, weighing 2mg of the sample, putting the sample into a small centrifugal tube, adding 300ml of absolute ethyl alcohol and 30ml of perfluorinated resin, and performing ultrasonic treatment for 1 hour to prepare slurry; uniformly dripping the slurry on the carbon paper by using a liquid-transfering gun, wherein the dripping area is 1cm 2 (the specification of the carbon paper is 1 × 1.5 cm); and (3) putting the carbon paper into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the electrode slice. Then in a three-electrode system, at VSe 2 The sample is a working electrode, the Pt sheet is a counter electrode, the Ag/AgCl is a reference electrode, and the sample passes through an electrochemical workstationThe electrocatalytic performance of the catalyst is tested by a Linear Sweep Voltammetry (LSV).
FIG. 6 is a polarization curve obtained at a scan rate of 5mV/s for three samples and a commercial 20% Pt/C catalyst obtained in examples 1-3; FIG. 7 is the Tafel slopes corresponding to the polarization curves obtained for the three samples obtained in examples 1-3 and a commercial 20% Pt/C catalyst at a scan rate of 5 mV/s. Table 1 shows the overpotential values and corresponding Tafel slope values for the three samples obtained in examples 1 to 3 and a commercial 20% Pt/C catalyst at a current density of 10 mA. As can be seen from the figure, the best catalytic performance is VSe at a current density of 10mA 1.8 The overpotential of the sample is only 160mV, and VSe 1.6 And VSe 2.0 The overpotential of (a) is 189mV and 247mV, respectively. The corresponding Tafel slope also indicates VSe 1.8 The catalytic performance of (a) is the best, and the value is only 85mV/dec. The invention VSe 2 When the two-dimensional material is applied to the electrocatalyst, the defects are distributed in the unique layered structure of the two-dimensional material, so that the number of active sites is increased, and the electrocatalytic hydrogen evolution overpotential of the two-dimensional material can be adjusted from 160mV to 247mV. It is worth noting that the invention also prepares two-dimensional materials with molar ratio of Se and V of 1.2 and 1.4, and the electrocatalytic activity is studied to find that the catalytic performance is far inferior to VSe 2.0 The sample, probably because the existence of a large number of defects, destroys the lattice periodicity of the two-dimensional material, so that the electrical properties of the material that are beneficial for catalytic activity are destroyed, and the catalytic activity is reduced. This indicates that the introduction of a suitable amount of Se vacancy defects can improve the catalytic performance of the material.
TABLE 1
Example 4
This example is different from example 1 in that: in the step 1, 0.2g of high-purity vanadium powder and 0.496g of high-purity selenium powder are weighed (the molar ratio of V to Se is 1.6; in the step 3, the temperature is kept at 700 ℃ for 24h, and after the reaction is finished, the reaction product is taken out, so that the molar ratio of V to Se is 1: 1.6. The rest of the procedure was the same as in example 1.
Example 5
This example is different from example 1 in that: in the step 1, 0.2g of high-purity vanadium powder and 0.558 g high-purity selenium powder are weighed (the molar ratio of V to Se is 1.8; and 3, preserving the heat at 850 ℃ for 72h, and taking out after the reaction is finished to obtain the material with the molar ratio of V to Se being 1: 1.8. The remaining procedure was the same as in example 1.
Example 6
This example is different from example 1 in that: in the step 1, 0.2g of high-purity vanadium powder and 0.62g of high-purity selenium powder are weighed (the molar ratio of V to Se is 1:2); and 3, preserving the heat at 900 ℃ for 72 hours, and taking out after the reaction is finished to obtain the material with the molar ratio of V to Se being 1:2. The remaining procedure was the same as in example 1.
Example 7
This example is different from example 1 in that: in the step 1, 0.6g of high-purity vanadium powder and 1.488 g high-purity selenium powder are weighed (the molar ratio of V to Se is 1; and 3, preserving the heat at 700 ℃ for 24 hours, and taking out after the reaction is finished to obtain the material with the molar ratio of V to Se being 1: 1.6. The rest of the procedure was the same as in example 1.
Example 8
This example is different from example 1 in that: in the step 1, 0.6g of high-purity vanadium powder and 1.674 g high-purity selenium powder are weighed (the molar ratio of V to Se is 1.8; and 3, preserving the heat at 850 ℃ for 24 hours, and taking out after the reaction is finished to obtain the material with the molar ratio of V to Se being 1: 1.8. The remaining procedure was the same as in example 1.
Example 9
This example is different from example 1 in that: in the step 1, 0.6g of high-purity vanadium powder and 1.86g of high-purity selenium powder are weighed (the molar ratio of V to Se is 1:2); and 3, preserving the heat at 900 ℃ for 72 hours, and taking out after the reaction is finished to obtain the material with the molar ratio of V to Se being 1:2. The rest of the procedure was the same as in example 1.
Claims (2)
1. Two-dimensional material VSe with different defect degrees 2 The method for producing (1), characterized by comprising the steps of;
step 1, weighing vanadium powder and selenium powder as raw materials, mixing and grinding the raw materials, and transferring the mixture into a quartz tube; wherein the molar ratio of the vanadium powder to the selenium powder is 1: (1.6-2.0);
step 2, carrying out vacuum pumping treatment on the quartz tube filled with the vanadium powder and the selenium powder in the step 1, and carrying out tube sealing treatment by adopting oxygen/acetylene flame; after the tube is sealed by oxygen/acetylene flame, the vacuum degree in the tube is 5-20 Pa;
step 3, vertically placing the sealed vacuum quartz tube in the step 2 into a vertical furnace, heating to 700-900 ℃ in the air atmosphere, preserving the heat for 24-72 hours at 700-900 ℃, cooling to 400 ℃ after the reaction is finished, naturally cooling to room temperature, and taking out to obtain the two-dimensional material VSe with different defect degrees 2 ；
The two-dimensional material VSe obtained can be regulated and controlled by changing the molar ratio of the vanadium powder to the selenium powder 2 The degree of defect of (a).
2. The method of claim 1, wherein the two-dimensional material VSe has different defect levels 2 Application in electrocatalytic hydrogen production.
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