CN111604062B - Ultra-small hollow cube nano material, preparation method thereof and application thereof in electrocatalytic hydrogen evolution - Google Patents

Ultra-small hollow cube nano material, preparation method thereof and application thereof in electrocatalytic hydrogen evolution Download PDF

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CN111604062B
CN111604062B CN202010510684.5A CN202010510684A CN111604062B CN 111604062 B CN111604062 B CN 111604062B CN 202010510684 A CN202010510684 A CN 202010510684A CN 111604062 B CN111604062 B CN 111604062B
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small
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hollow
zif
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CN111604062A (en
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罗佳冰
周炎
张军
王雪媛
王淑涛
脱永笑
贾翠萍
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China University of Petroleum East China
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    • 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
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

The invention relates to an ultra-small hollow cube nanomaterial, a preparation method thereof and application thereof in electrocatalytic hydrogen evolution, and belongs to the field of nanomaterial synthesis. The invention synthesizes the ultra-small Co from the ZIF-67 precursor through a simple one-step hydrothermal method at 200 ℃ for 12 hours 3 S 4 ‑MoS 2 Hollow cube nanocomposite. The nano material synthesized by the invention has an ultra-small special structure, the experimental process is simple and feasible, the environment is friendly, the hollow structure can provide a larger specific surface area, the electron transmission is accelerated, the excellent hydrogen evolution performance and good stability are realized, and the potential practical value is higher.

Description

Ultra-small hollow cube nano material, preparation method thereof and application thereof in electrocatalytic hydrogen evolution
Technical Field
The invention relates to a preparation method of an ultra-small hollow cube nano material, in particular to a hollow cube nano composite material formed by an ultra-small structure, belonging to the field of nano material synthesis.
Background
Hydrogen energy has become a new energy source to prevent the energy and environmental crisis caused by the consumption of traditional fossil fuels. The electrolytic water is also called electrochemical water cracking, and is a high-efficiency direct hydrogen production method. Usually consisting of two half reactions, hydrogen evolution and oxygen evolution, and electrocatalysts are often required to reduce the potential required to drive the water electrolysis process. While platinum is the most effective catalyst for hydrogen evolution reactions, its application potential is limited by rarity and high price, and therefore the development of efficient, stable, low cost electrocatalysts for hydrogen evolution reactions has become a major concern.
Transition metal compounds, such as transition metal carbides, sulfides, selenides, phosphides, and borides, exhibit excellent properties in promoting hydrogen evolution reactions, wherein transition metal sulfides exhibit excellent catalytic properties due to their unique electronic structures. Molybdenum disulfide is considered an excellent electrocatalyst due to its good surface energy matching the absorption of hydrogen species. And compared with binary metal compounds, ternary metal compounds have better catalytic activity due to more active centers, synergistic effects and tunable electronic structures.
Construction of hollow structures is another effective method of increasing the activity of electrocatalysts. In recent years, metal-organic frameworks have been used as an ideal precursor for the synthesis of transition metal compounds. For example: CN110681407a discloses a Fe doped co1.11te2@ncntfs nanocomposite and a preparation method thereof. The method comprises the following steps: adding ferric nitrate into a ZIF-67 precursor, taking ethanol as a reaction solvent, and stirring at room temperature to obtain a Fe-doped ZIF-67 precursor; and (3) taking tellurium powder as a tellurium source, and calcining the Fe-doped ZIF-67 precursor under an Ar/H2 mixed atmosphere to obtain the Fe-doped Co1.11Te2@NCNTFs nanocomposite. CN110538662a discloses a method for preparing cobalt doped rhenium disulfide nanosheet array for electrocatalytic hydrogen evolution, which comprises the following steps: adding 2-methylimidazole aqueous solution into cobalt nitrate hexahydrate aqueous solution, and immersing a piece of acid-treated carbon cloth into the mixed solution; after reacting for a period of time, sampling and cleaning with deionized water; growing in the same solution for a period of time to obtain ZIF-67 nanometer array sample named ZIF-67/CC, and finally, cleaning the sample, and dryingAnd (5) processing. Dissolving cobalt nitrate hexahydrate in a mixed solution of ultrapure water and ethanol, and putting the prepared ZIF-67/CC into the mixed solution for hydrolysis to obtain a product cobalt hydroxide nano array Co (OH) 2 CC; obtaining the product Co-ReS 2 /CC. However, the preparation of the compound with the special structure has certain difficulty, so that the nano material with the special structure is further synthesized by taking the metal organic framework as a precursor and is applied to electrocatalytic hydrogen evolution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hollow cube nanocomposite material formed by an ultra-small structure, which has the advantages that the ultra-small special structure can accelerate the electron transmission rate, the hollow cube structure provides a larger specific surface area, and the high efficiency and the high capacity of hydrogen separation in the electrocatalytic process can be realized, so that the hollow cube nanocomposite material has higher application value in synthesizing hydrogen clean energy.
The invention also provides a preparation method of the hollow cube nanocomposite material with the ultra-small structure and application of the hollow cube nanocomposite material in electrocatalytic hydrogen evolution.
The technical scheme of the invention is as follows:
an ultra-small hollow cube nano-material is Co 3 S 4 -MoS 2 The size of the composite material, hollow cube nano structure, is 300-500 nm.
According to the invention, preferably, the Co 3 S 4 -MoS 2 Lattice distance in the composite material corresponds to Co 3 S 4 (440)、Co 3 S 4 (400)、Co 3 S 4 (311) And MoS 2 (002). Under the high resolution condition, the cobaltosic tetrasulfide and the molybdenum disulfide are in an adhesion state.
According to the present invention, preferably, the X-ray photoelectron spectrum of the ultra-small hollow cubic nanomaterial shows peaks containing five components of C1S, O1S, mo3d, co2p and S2p, and in the Co region, 781.84eV (Co 2p 3/2 ) And 798.03eV (Co 2 p) 1/2 ) Corresponding to Co 3 S 4 A phase; in the Mo3d region, two satellite peaks appear at 803.49eV and 786.17eV, respectivelyCorresponding to Co 2+ And Co 3+ Two main peaks are located at 232.13eV and 228.89eV, respectively, corresponding to Mo3d 3/2 And Mo3d 5/2 Belongs to Mo 4+ The method comprises the steps of carrying out a first treatment on the surface of the In the S2p region, the Co-S bond and the Mo-S bond have two sets of peaks, one set located at 161.56eV and 164.31eV, respectively, corresponding to Co-S bond S2p 3/2 And S2p 1/2 A track; the other group is located at 161.83 and 162.94eV, corresponding to S2p in the Mo-S bond 3/2 And S2p 1/2 A track.
According to the invention, the preparation method of the ultra-small hollow cube nanomaterial comprises the following steps:
and (3) dispersing ZIF-67 into an ethanol solution, adding sodium molybdate dihydrate and thioacetamide, and performing one-step hydrothermal reaction to obtain the hollow cube nanomaterial with the ultra-small structure.
According to the invention, preferably, the ZIF-67 is synthesized by 2-methylimidazole methanol solution and cobalt nitrate hexahydrate methanol solution at room temperature;
further preferably, the ZIF-67 is synthesized as follows:
mixing cobalt nitrate hexahydrate methanol solution and 2-methylimidazole methanol solution, stirring, standing at room temperature for 24 hours, centrifuging the purple product after the reaction, and drying to obtain ZIF-67. Preferably, the concentration of cobalt nitrate hexahydrate and 2-methylimidazole are 5mmol L, respectively -1 And 40mmol L -1 。
According to the invention, preferably, the mass ratio of ZIF-67, sodium molybdate dihydrate and thioacetamide is 1: (0.7-1): (2.4-2.8), more preferably 1:0.83:2.57.
According to the invention, preferably, the hydrothermal reaction temperature is 190-205 ℃ and the reaction time is 10-14h; further preferably, the hydrothermal reaction temperature is 200℃and the reaction time is 12 hours.
According to the invention, preferably, the reaction is finished and cooled to room temperature, and the ultra-small Co is obtained by centrifugal cleaning and drying 3 S 4 -MoS 2 A hollow composite material.
The invention also provides application of the ultra-small hollow cube nanomaterial in electrocatalytic hydrogen evolution.
The invention takes ZIF-67 as a precursor, synthesizes a hollow cube with an ultra-small structure through a simple one-step hydrothermal reaction, and has the ultra-small special structure capable of accelerating electron transmission rate, providing a large specific surface area for the hollow cube structure, realizing high-efficiency and high-capacity hydrogen precipitation in the electrocatalytic process, and an experimental flow is shown in figure 16.
The hydrogen evolution performance of the present invention was tested as follows: dispersing 5mg of catalyst sample into 500 mu l of ethanol, adding 20 mu l of Nafion solution to form uniform slurry, carrying out ultrasonic treatment for 1h, and then dripping 100 mu l of mixed solution into pretreated carbon paper, wherein the load concentration is 1mgcm -2 As a working electrode.
The polarization curve (LSV) and cyclic voltammetry Curve (CV) of the invention are tested in a solution of 1.0M KOH by using a CHI660E electrochemical workstation, ag/AgCl (3M KCl) is used as a reference electrode, a graphite electrode is used as a counter electrode, the electrolyte is pre-filled with nitrogen for 30min to remove oxygen before each experiment, and the sweeping speed is set to be 5 mV.s -1 And a stable polarization curve was obtained after 20 scans.
In the alternating current impedance (EIS) test of the present invention, the open circuit potential parameter was set to-0.176V (vs. Ag/AgCl electrode) and the frequency was set from 100000Hz to 0.01Hz.
The overpotential (eta) of the invention is opposite to log (j) to obtain a Tafil curve, and then the Tafil slope is obtained to evaluate the dynamic performance of the catalyst for electrocatalytic hydrogen production.
All potential values in the experiment of the invention are corrected by the standard hydrogen electrode, and the polar potential calibration equation is as follows:
E RHE ＝E Ag/AgCl +0.059pH+E 0 Ag/AgCl (E 0 Ag/AgCl ＝0.209V)
compared with the prior art, the invention has the following beneficial effects:
1. the invention synthesizes a hollow cube nano composite material with a super-small special structure by taking ZIF-67 as a precursor for the first time, firstly synthesizes ZIF-67 by 2-methylimidazole methanol solution and cobalt nitrate hexahydrate methanol solution at room temperature, disperses a synthesized sample into ethanol solution, adds sodium molybdate dihydrate and thioacetamide, and obtains the hollow cube nano material with the super-small structure by one-step simple hydrothermal reaction. The nano material synthesized by the invention has an ultra-small special structure, the experimental process is simple and feasible, the environment is friendly, and the ultra-small special structure can accelerate the electron transmission rate and the hollow cube structure provides a larger specific surface area.
2. The invention discovers through linear scanning curve performance test: the hollow cube nanocomposite material formed by the ultra-small structure has excellent hydrogen evolution performance, and particularly has excellent hydrogen evolution performance with molybdenum disulfide (MoS) 2 ) Tricobalt tetrasulfide (Co) 3 S 4 ) Compared with the method, under the same current density, high efficiency and high capacity of hydrogen gas separation in the electrocatalytic process can be realized, so that the method has higher application value in electrocatalytic hydrogen separation. Good stability, and current density of 10mA cm -2 When the overpotential is only 105mV.
Drawings
FIG. 1 is a transmission electron micrograph of a zeolitic imidazoles framework material 67 nanomaterial obtained in example 1;
FIG. 2 shows the ultra-small Co obtained in example 2 3 S 4 -MoS 2 Transmission electron microscope pictures of the hollow nano-materials;
FIG. 3 shows the ultra-small Co obtained in example 2 3 S 4 -MoS 2 High resolution transmission electron microscope pictures of the hollow nano materials;
FIG. 4 shows the ultra-small Co obtained in example 2 3 S 4 -MoS 2 X-ray diffraction patterns of hollow nanomaterials compared to example 1, comparative examples 7, 8;
FIG. 5 shows the ultra-small Co obtained in example 2 3 S 4 -MoS 2 High resolution spectra of hollow nanomaterial X-ray photoelectron spectroscopy (a) and Co2p (b), mo3d (c) and S2p (d);
FIG. 6 shows the ultra-small Co obtained in example 2 3 S 4 -MoS 2 The graph (a) of the hydrogen evolution performance test of the hollow nano material is a linear scanning curve, the graph (b) is a cyclic voltammetry curve at different scanning speeds, the graph (c) is an alternating current impedance curve, and the graph (d) is tafel-terraeThe line (e) is 100mA cm -2 Constant current stability test under current density;
FIG. 7 is a very small Co obtained in comparative example 1 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 8 is a very small Co obtained in comparative example 2 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 9 is a very small Co obtained in comparative example 3 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 10 shows the ultra-small Co obtained in comparative example 4 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 11 is a very small Co obtained in comparative example 5 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 12 is a very small Co obtained in comparative example 6 3 S 4 -MoS 2 A transmission electron microscope picture of the hollow nano material;
FIG. 13 is Co obtained in comparative example 7 3 S 4 Scanning electron microscope pictures of the nano materials;
FIG. 14 shows the MoS obtained in comparative example 8 2 Scanning electron microscope pictures of the nano materials;
FIG. 15 shows the ultra-small Co prepared in example 2 and comparative examples 1-6 3 S 4 -MoS 2 And comparing the polarization curves of the hollow nano materials with the pictures.
FIG. 16 is a very small Co of example 2 3 S 4 -MoS 2 A preparation flow chart of the hollow nanometer material.
Detailed Description
The method for preparing hollow cubic nanomaterial composed of ultra-small structures according to the present invention will be described in detail with reference to the following specific embodiments and examples.
In the examples below, the main experimental reagents and instruments used are listed below:
cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·2H 2 O), 2-methylimidazole (C) 4 H 6 N 2 ) Methanol, sodium molybdate dihydrate (Na 2 MoO 4 ·2H 2 O), thioacetamide (CH) 3 CSNH 2 ) Absolute ethanol, nafion (5 wt%), 20% Pt/C, magnetic stirrer (Color quick [ white)]) Bench-top high-speed centrifuges (TG 16-WS), analytical electronic balances (BS 210S), electrothermal blowing dry boxes (DHG-9015A), ultrasonic cleaners (KQ 2200B type), X-ray diffractometers (X' Pert PROMPD), transmission electron microscopes (JEM-2100 (UHR), X-ray photoelectron spectroscopy (JEOL Ltd), electrochemical workstations (CHI 660E).
Example 1
Weighing 1.455g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole, respectively dissolving in 100mL of methanol solution, pouring the cobalt nitrate hexahydrate methanol solution into the 2-methylimidazole methanol solution under the action of strong stirring, stirring for 5min, standing the mixed solution at room temperature for 24h, centrifuging and washing the obtained purple sample with methanol for 3 times, and drying in vacuum to obtain ZIF-67 for later use;
the transmission electron micrograph of the ZIF-67 precursor obtained in this example is shown in FIG. 1, and ZIF-67 has a cubic structure and a size of 300 to 500nm.
Example 2
Weighing 145.7mg ZIF-67, dispersing into 10mL ethanol solution, adding 120.975mg sodium molybdate dihydrate and 375mg thioacetamide into the solution, performing hydrothermal reaction at 200deg.C for 12h, cooling to room temperature, centrifuging with ionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
Example 3
Weighing 145.7mg ZIF-67, dispersing into 10mL ethanol solution, adding 120.975mg sodium molybdate dihydrate and 375mg thioacetamide into the solution, performing hydrothermal reaction at 190 ℃ for 13h, cooling to room temperature, centrifuging with ionized water and ethanol, washing, and vacuum drying to obtain ultra-small Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
Example 4
Weighing 145.7mg ZIDispersing F-67 in 10mL ethanol solution, adding 120.975mg sodium molybdate dihydrate and 375mg thioacetamide into the solution, performing hydrothermal reaction at 205 ℃ for 10h, cooling to room temperature, centrifuging with ionized water and ethanol, washing, and vacuum drying to obtain ultra-small Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
Example 5
Weighing 145.7mg ZIF-67, dispersing into 10mL ethanol solution, adding 102mg sodium molybdate dihydrate and 350mg thioacetamide into the solution, performing hydrothermal reaction at 200 ℃ for 12h, cooling to room temperature, centrifuging and washing with ionized water and ethanol, and vacuum drying to obtain ultra-small Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
Example 6
Weighing 145.7mg ZIF-67, dispersing into 10mL ethanol solution, adding 145.7mg sodium molybdate dihydrate and 407mg thioacetamide into the solution, performing hydrothermal reaction at 200 ℃ for 12h, cooling to room temperature, centrifuging and washing with ionized water and ethanol, and vacuum drying to obtain ultra-small Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
Test example 1,
For the ultra-small Co obtained in example 2 3 S 4 -MoS 2 The hollow cube nanomaterial was characterized as follows:
transmission electron microscope: the obtained ultra-small Co 3 S 4 -MoS 2 The transmission electron microscope photograph of the composite material is shown in FIG. 2, co 3 S 4 -MoS 2 The metal organic framework structure remains unchanged and the size is about 300-500 nm, but compared with ZIF-67, co 3 S 4 -MoS 2 The catalyst surface became rough, and a hollow structure was obtained as seen from the broken dodecahedral block structure.
High resolution transmission electron microscope: the high resolution photograph is shown in figure 3, and the prepared ultra-small Co 3 S 4 -MoS 2 Lattice distance in the composite material corresponds to Co 3 S 4 (440)、Co 3 S 4 (400)、Co 3 S 4 (311) And MoS 2 (002) Under the high resolution condition, the cobaltosic sulfide and the molybdenum disulfide are in an adhesion state, and the ultra-small molybdenum disulfide can be obtained.
X-ray diffraction pattern: FIG. 4 is a very small Co 3 S 4 -MoS 2 X-ray diffraction patterns compared with example 1, comparative examples 7 and 8. The characteristic diffraction peak belonging to ZIF-67 disappears, and some new blurred peaks appear, which indicates that the ZIF-67 is completely transformed, and only two diffraction peaks are allocated to Co 3 S 4 Corresponding to (311) and (400) lattice planes.
X-ray photoelectron spectroscopy: as can be seen from FIG. 5a, co 3 S 4 -MoS 2 The composite material contains peaks of five components of C1S, O1S, mo3d, co2p and S2 p. In the Co region (FIG. 5 b), 781.84eV (Co 2p 3/2 ) And 798.03eV (Co 2 p) 1/2 ) Corresponding to Co 3 S 4 And (3) phase (C). In the Mo3d region (fig. 5 c), two satellite peaks appear at 803.49eV and 786.17eV, respectively, corresponding to Co 2+ And Co 3+ Two main peaks are located at 232.13eV and 228.89eV, respectively, corresponding to Mo3d 3/2 And Mo3d 5/2 Belongs to Mo 4+ . In the S2p region (FIG. 5 d), the Co-S bonds and the Mo-S bonds have two sets of peaks, one set at 161.56eV and 164.31eV, respectively, corresponding to Co-S bonds S2p 3/2 And S2p 1/2 A track; the other group is located at 161.83 and 162.94eV, corresponding to S2p in the Mo-S bond 3/2 And S2p 1/2 A track.
Test example 2,
For the ultra-small Co prepared in example 2 3 S 4 -MoS 2 The electrochemical hydrogen production performance of the hollow cube nanomaterial was tested as follows:
the linear scanning voltammetry is to disperse 5mg of catalyst sample into 500 mu l of ethanol, add 20 mu l of Nafion solution to form uniform slurry, carry out ultrasonic treatment for 1h, then drop 100 mu l of mixed solution into pretreated carbon paper, and load the solution with the concentration of 1mg cm -2 As a working electrode.
Polarization Curve (LSV) and Cyclic Voltammogram (CV) were performed in a 1.0M KOH solution using a CHI660E electrochemical workstationTesting, using Ag/AgCl (in 3M KCl) as a reference electrode, using a graphite electrode as a counter electrode, introducing nitrogen into the electrolyte for 30min in advance before each experiment to deoxidize, and setting the sweeping speed to be 5 mV.s -1 And a stable polarization curve was obtained after 20 scans. Ultra-small Co of example 2 3 S 4 -MoS 2 The hydrogen evolution performance of the hollow nanocomposite is shown in FIG. 6, the graph (a) of FIG. 6 is a linear scanning curve (LSV), the graph (b) of FIG. 6 is a cyclic voltammogram at different sweep rates of 5-40 mV.s -1 . As can be seen from FIG. 6 (a), ultra-small Co 3 S 4 -MoS 2 The hydrogen evolution performance of the hollow nano composite material is superior to that of cobaltosic sulfide and molybdenum disulfide.
An alternating current impedance (EIS) test, the open circuit potential parameter was set at-0.176V (vs. Ag/AgCl electrode) and the frequency was set from 100000Hz to 0.01Hz. Ultra-small Co of example 2 3 S 4 -MoS 2 As shown in FIG. 6 (c), the AC impedance image of the hollow nanocomposite material shows that FIG. 6 (c) shows that the ultra-small Co 3 S 4 -MoS 2 Hollow nanocomposites have a lower electron transfer resistance.
The overpotential (η) versus log (j) yields a tafel curve, and then the tafel slope is calculated to evaluate the catalyst's electrocatalytic hydrogen production kinetics. As can be seen from FIG. 6 (d), ultra-small Co 3 S 4 -MoS 2 The hollow nanocomposite material has a smaller Tafil slope of 42.3mV dec -1 。
Ultra-small Co of example 2 3 S 4 -MoS 2 Hollow nanocomposite at 100mA cm -2 Testing constant current stability at power density the test is shown in figure 6 (e). From FIG. 6 (e), it can be seen that the ultra-small Co 3 S 4 -MoS 2 The hollow nano composite material has good stability in hydrogen evolution reaction.
Comparative example 1
Weighing ZIF-67242.85mg, dispersing into 10mL ethanol solution, weighing 41.13mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 200deg.C for 12 hr, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
As shown in FIG. 7, the transmission electron microscope image of the catalyst obtained in this comparative example shows that the thickness of the edge-synthesized molybdenum disulfide platelet was about 20nm as compared with example 2.
Comparative example 2
Weighing ZIF-67.7 mg, dispersing into 10mL ethanol solution, weighing 200.8185mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 200deg.C for 12 hr, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
As shown in FIG. 8, the transmission electron microscope image of the catalyst obtained in this comparative example shows that the thickness of the edge-synthesized molybdenum disulfide platelet was about 40nm as compared with example 2.
Comparative example 3
Weighing ZIF-67.7 mg, dispersing into 10mL ethanol solution, weighing 120.975mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 150deg.C for 12 hr, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
As shown in FIG. 9, the transmission electron microscope image of the catalyst obtained in this comparative example shows that the thickness of the edge-synthesized molybdenum disulfide platelet was about 15nm, which indicates that the reaction temperature was too low to be completely vulcanized, as compared with example 2.
Comparative example 4
Weighing ZIF-67.7 mg, dispersing into 10mL ethanol solution, weighing 120.975mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 210 ℃ for 12h, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain ultra-small Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
The transmission electron microscope picture of the catalyst obtained in this comparative example is shown in fig. 10, and the metal-organic frameworks have collapsed in comparison with example 2, demonstrating that an excessive temperature will cause collapse of the metal-organic frameworks.
Comparative example 5
Weighing ZIF-67.7 mg, dispersing into 10mL ethanol solution, weighing 120.975mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 200deg.C for 6h, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
As shown in FIG. 11, the transmission electron microscope picture of the catalyst obtained in this comparative example shows that the thickness of the edge-synthesized molybdenum disulfide platelet is about 15nm, compared with example 2, and that the insufficient vulcanization is caused by too short vulcanization time.
Comparative example 6
Weighing ZIF-67.7 mg, dispersing into 10mL ethanol solution, weighing 120.975mg sodium molybdate dihydrate and 375mg thioacetamide, adding into the solution, performing hydrothermal reaction at 200deg.C for 24 hr, cooling to room temperature, centrifuging with deionized water and ethanol, washing, and vacuum drying to obtain microminiature Co 3 S 4 -MoS 2 Hollow cubic nanomaterial.
The transmission electron microscope picture of the catalyst obtained in this comparative example is shown in fig. 12, and the metal-organic frameworks have collapsed in comparison with example 2, and it is also demonstrated that the reaction time course will cause collapse of the metal-organic frameworks.
Comparative example 7
ZIF-67.7 mg was weighed and dispersed in 10mL of ethanol solution, 375mg of thioacetamide was weighed and added to the solution, the mixture was subjected to hydrothermal reaction at 200℃for 12 hours, cooled to room temperature, centrifugally washed with deionized water and ethanol, and vacuum-dried to obtain tricobalt tetrasulfide (Co) 3 S 4 ) Cubic nanomaterial.
Tricobalt tetrasulfide (Co) obtained in this comparative example 3 S 4 ) As shown in FIG. 13, a scanning electron micrograph of Co 3 S 4 Is a dodecahedron block structure, and is a microminiature Co 3 S 4 -MoS 2 Compared with the hollow nano material, the hollow nano material exposes more active sites and becomes the main part of electrocatalytic hydrogen evolutionFactors are important.
Comparative example 8
120.975mg of sodium molybdate dihydrate and 375mg of thioacetamide are weighed and dispersed into 10mL of ethanol solvent, the mixture is subjected to hydrothermal reaction at 200 ℃ for 12 hours, cooled to room temperature, centrifugally washed by deionized water and ethanol, and dried in vacuum to obtain molybdenum disulfide (MoS) 2 ) A platelet nanomaterial.
The comparative example yielded molybdenum disulfide (MoS 2 ) As shown in FIG. 14, the scanning electron micrograph of MoS 2 The material is a two-dimensional flaky material, and the agglomeration phenomenon causes less exposure of active sites, slows down the electron transmission speed, so that the material has lower electrochemical hydrogen evolution performance.
From the transmission electron micrographs of the catalysts obtained in the above examples and comparative examples, ultra-small Co prepared in example 2 3 S 4 -MoS 2 The morphology of the hollow nanocomposite is optimal, and the hydrogen production performance is far better than that of the samples prepared in comparative examples 1-6, which shows that the temperature time range and the material proportioning range are exceeded, and the effect is poor.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (5)

1. Preparation method of ultra-small hollow cube nano material, wherein the material is Co 3 S 4 -MoS 2 The composite material is a hollow cube nano structure, and the size of the composite material is 300-500 nm; the method comprises the following steps:
ZIF-67 is dispersed into ethanol solution, sodium molybdate dihydrate and thioacetamide are added, and hollow cubic nano material formed by ultra-small structure is obtained through one-step hydrothermal reaction;
the mass ratio of ZIF-67, sodium molybdate dihydrate and thioacetamide is 1: (0.7-1): (2.4-2.8), the hydrothermal reaction temperature is 190-205 ℃, and the reaction time is 10-14h;
the ZIF-67 synthesis steps are as follows:
mixing cobalt nitrate hexahydrate methanol solution and 2-methylimidazole methanol solution, stirring, standing at room temperature for 24 hr, centrifuging, and drying to obtain ZIF-67 with cobalt nitrate hexahydrate and 2-methylimidazole concentration of 5mmol L respectively -1 And 40mmol L -1 。
2. The method for preparing the ultra-small hollow cube nanomaterial according to claim 1, characterized in that the Co 3 S 4 -MoS 2 Lattice distance in the composite material corresponds to Co 3 S 4 （440）、Co 3 S 4 （400）、Co 3 S 4 (311) And MoS 2 （002）。
3. The method for preparing ultra-small hollow cubic nanomaterial according to claim 1, wherein the X-ray photoelectron spectroscopy of the ultra-small hollow cubic nanomaterial shows peaks containing five components of C1S, O1S, mo3d, co2p and S2p, and 781.84eV (Co 2p 3/2 ) And 798.03eV (Co 2 p) 1/2 ) Corresponding to Co 3 S 4 A phase; in the Mo3d region, two satellite peaks appear at 803.49eV and 786.17eV, respectively, corresponding to Co 2+ And Co 3+ Two main peaks are located at 232.13eV and 228.89eV, respectively, corresponding to Mo3d 3/2 And Mo3d 5/2 Belongs to Mo 4+ The method comprises the steps of carrying out a first treatment on the surface of the In the S2p region, the Co-S bond and the Mo-S bond have two sets of peaks, one set located at 161.56eV and 164.31eV, respectively, corresponding to Co-S bond S2p 3/2 And S2p 1/2 A track; the other group is located at 161.83 and 162.94eV, corresponding to S2p in the Mo-S bond 3/2 And S2p 1/2 A track.
4. The method for preparing ultra-small hollow cube nanomaterial according to claim 1, characterized in that the reaction junctionCooling to room temperature after the beams are bundled, and obtaining the ultra-small Co through centrifugal cleaning and drying 3 S 4 -MoS 2 A hollow composite material.
5. The use of the ultra-small hollow cube nanomaterial of claim 1 in electrocatalytic hydrogen evolution.
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CN113499474B (en) * 2021-05-31 2022-04-12 浙江大学 ZIF-67 modified hollow vanadium dioxide shell-core structure micro-nano composite and preparation method and application thereof
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