CN107159268B - Hollow molybdenum disulfide/molybdenum trioxide flower-shaped heterostructure nano material, preparation method and application - Google Patents
Hollow molybdenum disulfide/molybdenum trioxide flower-shaped heterostructure nano material, preparation method and application Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title abstract description 71
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract description 71
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 49
- 239000000047 product Substances 0.000 description 14
- 235000013877 carbamide Nutrition 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011805 ball Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000004729 solvothermal method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
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- 239000003792 electrolyte Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 241001530121 Trollius Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005485 electric heating Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002062 molecular scaffold Substances 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/51—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
The invention relates to hollow molybdenum disulfide/molybdenum trioxide (MoS)
2/MoO
3) The preparation method of the flower-ball-shaped heterostructure nano material comprises the following steps: 1) dispersing ammonium tetrathiomolybdate, urea and hydrazine hydrate in N, N-dimethylformamide to form a homogeneous solution; 2) transferring the solution obtained in the step 1) into a reaction kettle, and reacting at the temperature of 160-240 ℃ for 8-10 h; 3) after the reaction is finished, naturally cooling to room temperature, carrying out solid-liquid separation, washing and drying the precipitate to obtain the hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material. Hollow MoS of the invention
2/MoO
3The flower-ball-shaped heterostructure nano material can obviously improve the Hydrogen Evolution (HER) performance of the catalyst.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material chemistry and electrochemistry, and particularly relates to hollow molybdenum disulfide/molybdenum trioxide (MoS)
2/MoO
3) A flower-ball-shaped heterostructure nano material, a preparation method and application thereof in improving the hydrogen evolution performance of a catalyst.
Background
Since the 21 st century, energy and environmental problems have been highlighted, and people pay more attention to the development of clean new energy. The hydrogen energy is known as the most potential clean energy because of its advantages of high combustion heat value, wide application, environmental protection, etc. Accordingly, there has been a continuous effort to find a sustainable and efficient process for producing hydrogen. Electrocatalytic and photocatalytic hydrogen evolution reactions are considered to be the most important and efficient way to generate hydrogen. Noble metals such as platinum are considered to be the most effective Hydrogen Evolution Reaction (HER) catalysts to date. However, the high price and limited resources have largely hindered the use of noble metal-based catalysts. Therefore, the development of a hydrogen evolution reaction catalyst with high efficiency, low cost and high abundance is urgent.
In recent years, two-dimensional transition metal sulfide lamellar structures, particularly molybdenum disulfide (MoS)
2) Due to its excellent HER catalytic performance and low cost, it is the most promising non-noble metal catalyst. MoS
2Has a graphite-like layered structure, and the thinner the sheet layer is, the larger the specific surface area is, the stronger the adsorption capacity is, and the reaction activity and the catalytic performance are correspondingly improved. We have therefore intensively studied non-platinum electrochemical catalysts for the electrocatalytic hydrogen evolution. For example, MoS as shown by Xie et al (Xie J, Zhang H, LiS, et al, Advanced Materials, 2013, 25, 5807) in the 2013 report
2The nano-particles show outstanding electrocatalytic activity in the aspect of electrocatalytic hydrogen evolution, and the electrocatalytic activity is very close to Pt/C. By applying onto a conductive substrate (e.g. graphene nanoplatelets, Cu)
7S
4And porous Au), doping treatment (e.g., N-doped MoS)
2And C-doped MoS
2) And increasing MoS
2Active site of (3), etc. The catalyst will be applied to the exposure of the active edge of the water-splitting electrocatalyst. Of these, Xu et al (Xu J, Cui J, Guo C, et al, Angewandte Chemie, 2016,128, 6612) use Cu
7S
4As a substrate and using it as a MoS
2The conductive solid support of (1). In electrochemical tests, the current density of the nano-frame at an overpotential of 206mV reaches 200mA cm
-2. In the middle of Cu
7S
4The substrate improves MoS
2The activity of the catalyst is improved, and the electrochemical performance of the catalyst is improved.
However, the molybdenum disulfide has a complete structure and few exposed active edge sites, which affects the performance of the molybdenum disulfide as a hydrogen evolution reaction catalyst. To meet the requirements of commercial applications, researchers need to be on MoS
2The structure of (a) is regulated and optimized, including reduction of the number of layers, increase of exposed active sites, and the like. Molybdenum oxide (MoO)
x) Has better photocatalytic activity and better HER catalytic performance, lower cost, environmental protection and the like, and is often used as research in the aspect of catalysts. But the conductivity is low, the cycling stability is weak, and the performance of the catalyst is influenced. Thus, MoS was prepared
2And MoO
xThe composite catalyst will open up an effective way for improving the hydrogen evolution performance of the catalyst.
Disclosure of Invention
The invention aims to open up a new way and provide a hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material, a preparation method and application thereof in improving the hydrogen evolution performance of a catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
hollow MoS
2/MoO
3The preparation method of the flower-ball-shaped heterostructure nano material comprises the following steps:
1) dispersing ammonium tetrathiomolybdate, urea, hydrazine hydrate in N, N-Dimethylformamide (DMF) to form a homogeneous solution;
2) transferring the solution obtained in the step 1) into a reaction kettle, and carrying out solvothermal reaction at the temperature of 160-240 ℃ for 8-10 h;
3) after the reaction is finished, naturally cooling to room temperature, carrying out solid-liquid separation, washing and vacuum drying on the precipitate to obtain the hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material.
Specifically, in the step 1), the mass ratio of ammonium tetrathiomolybdate to urea is 1: 1-1.5. urea is an organic compound consisting of carbon, nitrogen, oxygen and hydrogen and having the molecular formula H
2NCONH
2(ii) a Also known as urea, carbamide, is a white solid. Too much or too little urea affects the flower-like structure of the nanomaterial product, and thus it is not preferable to obtain a flower-like nanomaterial. Preferably, 0.05-0.2 ml of hydrazine hydrate is added per 22mg of ammonium tetrathiomolybdate. Too much or too little hydrazine hydrate affects the internal structure of the nano material product, and the hollow nano material is not suitable to be obtained.
In the reaction in step 2), the reaction temperature is preferably 200 ℃ and the reaction time is preferably 10 hours.
Preferably, in the step 3), the solid-liquid separation can be centrifugal separation, the centrifugal rotation speed is 9000-10000 rpm, and the centrifugal time is 5-10 min.
Hollow MoS prepared by adopting method
2/MoO
3A flower-ball-shaped heterostructure nano material.
The hollow MoS
2/MoO
3The application of the flower-ball-shaped heterostructure nano material in improving the hydrogen evolution performance of the catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a new way for preparing hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material. Compared with chemical vapor deposition, template method and other methods, the method not only realizes the preparation of the hollow flower-ball-shaped heterostructure nano material, but also realizes the controllability of the cavity size of the flower ball and the number of petals, for example, the cavity size of the flower ball can be controlled by controlling the reaction time, and the growth of the petals can be monitored by controlling the reaction temperature。
2) Compared with the method for constructing the molybdenum disulfide-based nano material by using graphene oxide and other deposition methods, the method has the advantages of simple preparation process, small environmental pollution and easy batch preparation. Meanwhile, the hollow MoS obtained by the invention
2/MoO
3The flower-ball-shaped heterostructure nano material has excellent electrochemical performance.
3) The method has the advantages of simple process, simple and convenient operation, simple post-treatment and remarkable achievement.
4) The invention adopts the ammonium tetrathiomolybdate as the raw material, can be directly synthesized at high temperature, has simple process, high yield and wide source, and provides possibility for developing other non-expensive chalcogenide nano-framework catalysts.
Drawings
FIG. 1 is a schematic representation of the hollow MoS prepared in example 1
2/MoO
3TEM image of flower-ball-shaped heterostructure nanomaterial;
FIG. 2 shows a hollow MoS prepared in example 1
2/MoO
3An X-ray photoelectron energy spectrum of the nano material with the flower-ball-shaped heterostructure;
FIG. 3 shows a hollow MoS prepared in example 1
2/MoO
3X-ray diffraction spectrogram and Raman spectrum of the flower-ball-shaped heterostructure nano material;
FIG. 4 shows a hollow MoS prepared in example 1
2/MoO
3A polarization curve (a) and a corresponding tafel slope (b) of an electrochemical test of the flower-ball-shaped heterostructure nanomaterial;
FIG. 5 shows a hollow MoS prepared in example 1
2/MoO
3Graph of current density versus time for a flowerlike heterostructure nanomaterial in an acidic electrolyte at an overpotential of 200 mV;
FIG. 6 shows a hollow MoS prepared in example 1
2/MoO
3Testing the photocatalytic activity of the flower-ball-shaped heterostructure nano material;
FIG. 7 shows the hollow MoS prepared in examples 3-6 under 2h, 6h reaction conditions
2/MoO
3A transmission electron microscope image of the flower-ball-shaped heterostructure nanomaterial;
FIG. 8 shows an embodiment7-9 hollow MoS prepared at 120 ℃ and 160 DEG C
2/MoO
3And (3) a transmission electron microscope image of the flower-ball-shaped heterostructure nano-material.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the examples described below, ammonium tetrathiomolybdate (analytically pure) was purchased from sigma aldrich trade ltd and urea (analytically pure) was purchased from the research and development center for fine chemical engineering technology in Guangdong province.
Example 1
Hollow MoS
2/MoO
3The preparation method of the flower-ball-shaped heterostructure nano material comprises the following steps:
1) in a 100mL beaker, 22mg of ammonium tetrathiomolybdate and 22mg of urea were added, 35mL of N, N-dimethylformamide was added, and sonication was performed for 50min in a sonicator to form a homogeneous solution. Then adding 0.1ml of hydrazine hydrate, and carrying out ultrasonic treatment again for 30min in an ultrasonic cleaner;
2) transferring the solution obtained in the step 1) into a 100ml reaction kettle, putting the reaction kettle into an electric heating constant-temperature air-blast drying oven to perform solvothermal reaction, and keeping the temperature at 200 ℃ for 10 hours;
3) after the reaction is finished, naturally cooling to room temperature, centrifugally separating reaction liquid, washing and vacuum drying precipitates to obtain the hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material.
The obtained target product is hollow MoS
2/MoO
3A TEM image of the flower-ball-shaped heterostructure nanomaterial is shown in FIG. 1. An X-ray photoelectron spectrum (XPS) is shown in FIG. 2. The X-ray diffraction pattern (XRD) and Raman spectrum (Raman spectra) are shown in a and b of FIG. 3. The polarization curve for the electrochemical hydrogen evolution reaction is shown in a in fig. 4, and the corresponding tafel slope is shown in b in fig. 4. The catalytic activity of the current density as a function of time at an overpotential of 200mV, used in the electrocatalytic hydrogen evolution, is shown in FIG. 5. The catalytic activity for the photocatalytic hydrogen evolution aspect is shown in figure 6. TEM images of the products at different reaction times are shown in FIG. 7, but with different reactionsA TEM image of the product versus temperature is shown in FIG. 8.
The above characterization results show that: adopts ammonium tetrathiomolybdate as raw material, and obtains hollow MoS under the condition of solvothermal reaction
2/MoO
3The heterogeneous nano structure has a flower ball-shaped structure, the interior of the heterogeneous nano structure is hollow, and petals are assembled by a series of nano sheets (see figure 1). X-ray diffraction (XRD) pattern (fig. 3 a) demonstrates the presence of MoS in the flower-sphere-like nano-framework
2(JCPDS No. 37-1492) and MoO
3(JCPDS No. 89-5108). And MoS
2And MoO
3Compared with an XRD standard card, MoS exists in an XRD pattern of the sample
2Strong diffraction peak and MoO
3The weak diffraction peak of (2) indicates that the flower ball contains MoS
2And MoO
3。MoO
3Can be MoS
2With more defect rich sites. Raman spectroscopy (FIG. 3 b) at 142,212 and 375cm
-1The characteristic peak of (A) represents 1T-MoS
2. In contrast, 110, 126, 197, 238, 285 and 332cm
-1The characteristic peak at (A) is shown in 1T-MoS
2The presence of a certain amount of MoO in the body
3. Doped MoO
3MoS of (1)
2The material can be MoS
2More active sites are obtained, and the performance of the material is improved.
The prepared product is hollow MoS
2/MoO
3The performance of the three-electrode system is tested by loading the flower-ball-shaped heterostructure nano material on a glassy carbon electrode, and the electrolyte is 0.5M H
2SO
4. For HER, hollow MoS
2/MoO
3The flower-ball-shaped nanoscaffold exhibited a small overpotential of 110mV, above which the cathodic current rose rapidly (fig. 4 a). Compared with other structures of nano materials, the small overpotential makes the material of the invention more advantageous in practical application.
As a control, the invention also measured the MoS nanoplates prepared in comparative example 1, the calcined MoS prepared in example 2
2/MoO
3Nanomaterial products, whose initial potentials were 106mV and 73mV, respectively, showed poor HER activity. Hollow MoS of the invention
2/MoO
3The flower-ball shaped heterostructure nanomaterials had much smaller size than the highly crystalline samples (16)0-250 mV), indicating that the nano-material has good catalytic activity. To further understand the hollow MoS of the present invention
2/MoO
3Hydrogen evolution performance of flower-ball shaped nanomaterials, tafel plots of various catalysts were investigated in this application (fig. 4 b). Wherein, the hollow MoS of the invention
2/MoO
3The slope of the Tafel curve of the flower-like nanomaterial is 42mV/dec, which is lower than many MoS-based nanomaterials to date
2HER catalyst of (a), however calcined MoS prepared in example 2
2/MoO
3Nanomaterial product, MoS nanosheet, and commercial MoS
2Then the Tafel slope is higher, being 73, 106 and 186 mV/dec, respectively. The small tafel slope of such nanomaterials is advantageous for practical applications. As it will result in a faster increase in HER rate with increasing overpotential.
To explore the hollow MoS of the invention
2/MoO
3Durability of the flower-ball-shaped heterostructure nanomaterials in acidic environments, the application performed long-term cycling tests of static overpotentials (fig. 5). Continuous production of H in HER occurs when an overpotential of 200mV is applied
2And (4) carrying out molecular process. In fig. 5, a typical sawtooth shape occurs due to the alternating process of bubble accumulation and bubble release. The current density showed only slight sliding even after a long time of 11000 seconds, which is probably due to H
+Reduction of or H
2The covering of the electrode surface by the bubbles hinders the reaction-induced. The durability achieved in this work is comparable to other previously reported MoS
2The supported nanomaterial is better. It exhibits good long-term cycling performance to provide extremely strong electrochemical stability. To test the effect of photocatalysis on the structure, hollow MoS
2/MoO
3H of nanosphere flower
2The time course of the release is shown in fig. 6. The catalyst had almost 22 mmol g
-1h
-1H of (A) to (B)
2Comparison to commercial MoS
227 times higher. Preliminary measurements show that hollow MoS
2/MoO
3The globose flower shows better photocatalytic activity.
Comparative example 1
A preparation method of MoS nanosheets comprises the following steps:
1) ammonium tetrathiomolybdate and urea (mass ratio 1: 1) addition to DMF: other steps are the same as example 1, step 1);
2) solvent thermal reaction: same as example 1, step 2);
3) the product was washed, dried and collected as in step 3) of example 1.
The electrochemical test chart of the direct solvothermal reaction MoS nanosheet without adding hydrazine hydrate is shown in (a) in FIG. 4, and can be seen in the figure: compared with example 1, the overpotential is significantly greater than that of example 1 and the cathode current density is significantly smaller. This can result in: after hydrazine hydrate is added for treatment, the electrochemical hydrogen evolution performance is obviously improved.
Example 2
Calcined MoS
2/MoO
3The preparation method of the nano material comprises the following steps:
1) ammonium tetrathiomolybdate, urea, hydrazine hydrate were added to DMF: same as example 1, step 1);
2) solvent thermal reaction: same as example 1, step 2);
3) the product was washed, dried and collected as in step 3) of example 1.
4) Carbonizing at 350 deg.C for 2h, naturally cooling to room temperature to obtain black powder to obtain calcined MoS
2/MoO
3And (3) nano materials.
Examples 3 to 6
Hollow MoS
2/MoO
3The preparation method of the flower-ball-shaped heterostructure nano material comprises the following steps:
1) ammonium tetrathiomolybdate, urea, hydrazine hydrate were added to DMF: same as example 1, step 1);
2) solvothermal reaction, with the difference that the reaction time is 2, 4, 6 and 8 h: other steps are the same as those of step 2) of example 1;
the product was washed, dried and collected as in step 3) of example 1.
Examples 3 to 6 hollow MoS prepared
2/MoO
3Transmission Electron Microscope (TEM) image of flower-ball-shaped heterostructure nano materialAs shown in fig. 7. In the first stage, solid MoS grows within 2h
2/MoO
3The product has no cavity structure (a in figure 7). With the increase of the reaction time, after 6h of reaction, the ball flower gradually forms a cavity structure, and the cavity structure gradually becomes larger in the subsequent reaction, so that the hollow MoS is further formed
2/MoO
3And (4) ball-flower. The product cavity reached a maximum after 10h of reaction. And with the increase of time, the nanosheets on the globeflower are gradually dispersed from dense to dense, so that the contact area in the catalysis process is increased.
Examples 7 to 9
Hollow MoS
2/MoO
3The preparation method of the flower-ball-shaped heterostructure nano material comprises the following steps:
1) ammonium tetrathiomolybdate, urea, hydrazine hydrate were added to DMF: same as example 1, step 1);
2) the solvent thermal reaction is characterized in that the reaction temperature is respectively 120 ℃, 160 ℃ and 240 ℃: other steps are the same as those of step 2) of example 1;
3) the product was washed, dried and collected as in step 3) of example 1.
Examples 7 to 9 hollow MoS prepared
2/MoO
3A transmission electron microscopy TEM image of the flower-ball-shaped heterostructure nanomaterial is shown in fig. 8. TEM images show the evolution of the nanostructures with temperature. First, a solid sphere is formed at 120 ℃, and then a hollow MoS is gradually formed by increasing the reaction temperature
2/MoO
3And (4) nano ball flower.
Claims (5)
1. Hollow 1T-MoS directly used as photocatalytic and electrocatalytic hydrogen evolution catalyst
2/ MoO
3The flower-ball-shaped heterostructure nano material is characterized by being prepared through the following steps:
1) dispersing ammonium tetrathiomolybdate, urea and hydrazine hydrate in N, N-dimethylformamide to form a homogeneous solution;
2) transferring the solution obtained in the step 1) into a reaction kettle, and reacting at the temperature of 160-240 ℃ for 8-10 h;
3) after the reaction is finished, fromThen cooling to room temperature, carrying out solid-liquid separation, washing and drying the precipitate to obtain the hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nanomaterial;
in the step 1), the mass ratio of ammonium tetrathiomolybdate to urea is 1: 1-1.5; 0.05-0.2 ml of hydrazine hydrate is added per 22mg of ammonium tetrathiomolybdate;
the hollow MoS
2/MoO
31T-MoS of flower-ball-shaped heterostructure nano material
2The presence of a certain amount of MoO in the body
3Doped with MoO
3MoS of (1)
2Material to MoS
2More active sites are obtained, and the catalytic performance of the material is improved.
2. Hollow 1T-MoS as claimed in claim 1 directly as a photocatalytic and electrocatalytic hydrogen evolution catalyst
2/ MoO
3The flower-ball-shaped heterostructure nanomaterial is characterized in that the reaction temperature is 200 ℃ and the reaction time is 10 hours when the reaction is carried out in the step 2).
3. Hollow 1T-MoS as claimed in claim 1 directly as a photocatalytic and electrocatalytic hydrogen evolution catalyst
2/ MoO
3The flower-ball-shaped heterostructure nano material is characterized in that in the step 3), centrifugal separation is adopted for solid-liquid separation, the centrifugal rotation speed is 9000-10000 rpm, and the centrifugal time is 5-10 min.
4. Hollow 1T-MoS according to claim 1 directly as a catalyst for photocatalytic and electrocatalytic hydrogen evolution
2/ MoO
3The preparation method of the flower-ball-shaped heterostructure nano material is characterized by comprising the following steps of:
1) dispersing ammonium tetrathiomolybdate, urea and hydrazine hydrate in N, N-dimethylformamide to form a homogeneous solution;
2) transferring the solution obtained in the step 1) into a reaction kettle, and reacting at the temperature of 160-240 ℃ for 8-10 h;
3) after the reaction is finished, naturally cooling to room temperature, carrying out solid-liquid separation, washing and drying the precipitate to obtain the hollow MoS
2/MoO
3A flower-ball-shaped heterostructure nano material.
5. Hollow 1T-MoS according to claim 1 directly as a catalyst for photocatalytic and electrocatalytic hydrogen evolution
2/ MoO
3The application of the flower-ball-shaped heterostructure nano material in improving the hydrogen evolution performance of the catalyst.
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| CN109650448B (en) * | 2018-12-29 | 2021-08-17 | 广西大学 | alpha-MoO3Preparation method of hollow nanospheres |
| CN110048095A (en) * | 2019-03-25 | 2019-07-23 | 天津大学 | A method of preparing the molybdenum disulfide molybdenum dioxide composite material for sodium ion negative electrode material |
| CN110106519B (en) * | 2019-06-20 | 2021-04-02 | 温州大学 | TiO2/MoS2Preparation method of ultrathin nanosheet array composite material |
| CN111111729B (en) * | 2019-12-18 | 2021-08-13 | 西安交通大学 | Molybdenum disulfide-based nanocomposite material with hollow sandwich laminated structure and preparation method thereof |
| CN112899720B (en) * | 2021-01-15 | 2022-02-15 | 华中科技大学 | Mo/MoO with ampere-level current density hydrogen evolution performance2Preparation of in-plane heterojunctions |
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