CN107159268A - A kind of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material, preparation method and application - Google Patents
A kind of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material, preparation method and application Download PDFInfo
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- CN107159268A CN107159268A CN201710274412.8A CN201710274412A CN107159268A CN 107159268 A CN107159268 A CN 107159268A CN 201710274412 A CN201710274412 A CN 201710274412A CN 107159268 A CN107159268 A CN 107159268A
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 53
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 51
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 15
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 15
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 14
- 235000013877 carbamide Nutrition 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241001138444 Globularia alypum Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000260524 Chrysanthemum balsamita Species 0.000 description 2
- 235000005633 Chrysanthemum balsamita Nutrition 0.000 description 2
- 229910015711 MoOx Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 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
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical compound NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- ZJHHPAUQMCHPRB-UHFFFAOYSA-N urea urea Chemical compound NC(N)=O.NC(N)=O ZJHHPAUQMCHPRB-UHFFFAOYSA-N 0.000 description 1
Classifications
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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 present invention relates to a kind of hollow molybdenum disulfide/molybdenum trioxide（MoS2/MoO3）The preparation method of flower ball-shaped heterojunction structure nano material, comprises the following steps：1）Four thio ammonium molybdate, urea and hydrazine hydrate are scattered in N, N dimethylformamides to form homogeneous solution；2）By step 1）Resulting solution moves into reactor, and 8-10h is reacted in 160-240 DEG C；3）After reaction terminates, naturally cool to room temperature, separation of solid and liquid, precipitate it is scrubbed, be drying to obtain hollow MoS2/MoO3Flower ball-shaped heterojunction structure nano material.The hollow MoS of the present invention2/MoO3Flower ball-shaped heterojunction structure nano material can significantly improve the liberation of hydrogen of catalyst（HER）Performance.
Description
Technical field
The invention belongs to inorganic nano material chemistry and electrochemical technology field, and in particular to and a kind of hollow molybdenum disulfide/
Molybdenum trioxide（MoS2/MoO3）Flower ball-shaped heterojunction structure nano material, preparation method and its improve catalyst Hydrogen Evolution Performance in terms of
Application.
Background technology
Since 21 century, the energy and environmental problem become increasingly conspicuous, and development clean type new energy increasingly causes people's
Pay attention to.Hydrogen Energy is due to combustion heat value is high, purposes is wide, advantages of environment protection, is described as most potential cleaning energy
Source.Therefore, people have carried out unremitting effort and have prepared hydrogen to seek sustainable and effective method.Electrocatalytic hydrogen evolution react and
Photocatalysis evolving hydrogen reaction is considered as most important, the maximally effective approach for producing hydrogen.The noble metals such as platinum are considered as to be so far
Only maximally effective evolving hydrogen reaction（HER）Catalyst.But, your gold high price and limited resource largely hinder
Belong to the application of base catalyst.Therefore, the evolving hydrogen reaction catalyst for developing efficient, low cost and high abundance is extremely urgent.
In recent years, two-dimentional transient metal sulfide lamellar structure, especially molybdenum disulfide（MoS2）Due to excellent HER
Catalytic performance and low cost, as most promising non-precious metal catalyst.MoS2Layer structure with class graphite, Er Qieqi
Lamella is thinner, and specific surface area is bigger, adsorption capacity is stronger, reactivity and catalytic performance also can be improved accordingly.Therefore, Wo Menshen
Enter the non-platinum electrochemical catalyst in terms of have studied for electrocatalytic hydrogen evolution.For example, Xie et al.（Xie J, Zhang H, Li
S, et al., Advanced Materials, 2013, 25, 5807）The MoS shown in the report of 20132Nanometer
Particle performance goes out prominent electro catalytic activity in terms of electrocatalytic hydrogen evolution, and its electro catalytic activity is in close proximity to Pt/C.By
Conductive base（Such as graphene nanometer sheet, Cu7S4With porous Au）Upper loading catalyst, doping treatment（The MoS of such as N doping2
The MoS adulterated with C2）, and increase MoS2Avtive spot etc..Catalyst is by applied to water-splitting elctro-catalyst active margin
Exposure.And among this, Xu et al.（Xu J, Cui J, Guo C, et al., Angewandte Chemie, 2016,
128,6612）With Cu7S4For substrate, and it is used as MoS2Conductive solids carrier.In electro-chemical test, this nanometer frame
Current density of the frame under 206mV overpotential reaches 200mA cm -2.In this middle Cu7S4Substrate improves MoS2Activity,
Improve its chemical property.
But, molybdenum disulfide structural integrity, the active edge site of exposure is few, influences it as evolving hydrogen reaction catalyst
Performance.In order to adapt to the requirement of business application, researcher is needed to MoS2Structure regulated and controled and optimized, including reduce layer
Number, increase exposure avtive spot etc..Molybdenum oxide（MoOx）With preferable photocatalytic activity and preferable HER catalytic performances, and
And cost is relatively low, environment-friendly etc., is often used as the research in terms of catalyst.But its conductance is low, cyclical stability is weak, influence
The performance of catalyst.Therefore, MoS is prepared2And MoOxComposite catalyst will open up one for the Hydrogen Evolution Performance of raising catalyst to be had
Imitate route.
The content of the invention
Present invention aims at new way is opened up, there is provided a kind of hollow MoS2/MoO3Flower ball-shaped heterojunction structure nano material,
Preparation method and its application in terms of the Hydrogen Evolution Performance of catalyst is improved.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of hollow MoS2/MoO3The preparation method of flower ball-shaped heterojunction structure nano material, comprises the following steps：
1）Four thio ammonium molybdate, urea, hydrazine hydrate are scattered in N,N-dimethylformamide（DMF）In to form homogeneous solution；
2）By step 1）Resulting solution moves into reactor, and solvent thermal reaction is carried out in 160-240 DEG C, reacts 8-10h；
3）After reaction terminates, room temperature is naturally cooled to, separation of solid and liquid precipitates scrubbed, vacuum drying and produces hollow MoS2/MoO3
Flower ball-shaped heterojunction structure nano material.
Specifically, step 1）In, the mass ratio of four thio ammonium molybdate and urea is 1：1-1.5.Urea is one kind by carbon, nitrogen, oxygen
The organic compound constituted with hydrogen, molecular formula is H2NCONH2；Also known as urea, phosphoamide, carbonyl diamide urea, are white solid.Urea
Usage amount it is excessive or very few, influence can be produced on the flower ball-shaped structure of nano material product, the nanometer of flower ball-shaped should not be obtained
Material.The hydrazine hydrate of four thio ammonium molybdate addition 0.05-0.2ml per 22mg is advisable.Hydrazine hydrate is excessive or very few, can influence
The internal structure of nano material product, should not obtain hollow nano material.
Step 2）During middle reaction, reaction temperature is preferably 200 DEG C, and the reaction time is preferably 10h.
Preferably, step 3）In, separation of solid and liquid can from centrifuge, centrifugal rotational speed be 9000-10000 rpm, from
The heart time is 5-10 min.
Hollow MoS obtained by being prepared using the above method2/MoO3Flower ball-shaped heterojunction structure nano material.
Above-mentioned hollow MoS2/MoO3Flower ball-shaped heterojunction structure nano material answering in terms of catalyst Hydrogen Evolution Performance is improved
With.
Compared with prior art, beneficial effects of the present invention are embodied in：
1）Hollow MoS is prepared the invention provides a new way2/MoO3Flower ball-shaped heterojunction structure nano material.Compared to change
The methods such as vapour deposition process, masterplate method are learned, the inventive method not only realizes the system of hollow flower ball-shaped heterojunction structure nano material
It is standby, and bouquet cavity size and petal controllable quantity are realized, such as by controlling the reaction time, it is possible to achieve bouquet cavity is big
It is small controllable, and by controlling reaction temperature, the growth of petal can be monitored.
2）Compared with molybdenum disulfide based nano-material is built by sedimentations such as graphene oxides, preparation technology of the present invention
Simply, pollution environment is small, it is easy to prepared by batch.Meanwhile, the hollow MoS that the present invention is obtained2/MoO3Flower ball-shaped heterogeneous structural nano
Material has excellent chemical property.
3）The inventive method technique is simple, easy to operate, and post processing is simple, makes outstanding achievements.
4）The present invention uses four thio ammonium molybdate for raw material, and it can directly be synthesized at high temperature, and technique is simple, yield
Height, wide material sources provide possibility to open up the new chalkogenide nanometer framework catalyst for being used to develop other inexpensive.
Brief description of the drawings
Fig. 1 is that embodiment 1 prepares the hollow MoS of gained2/MoO3The TEM figures of flower ball-shaped heterojunction structure nano material；
Fig. 2 is that embodiment 1 prepares the hollow MoS of gained2/MoO3The x-ray photoelectron power spectrum of flower ball-shaped heterojunction structure nano material
Figure；
Fig. 3 is that embodiment 1 prepares the hollow MoS of gained2/MoO3The X-ray diffraction spectrogram of flower ball-shaped heterojunction structure nano material and
Raman spectrum；
Fig. 4 is that embodiment 1 prepares the hollow MoS of gained2/MoO3The polarization of the electro-chemical test of flower ball-shaped heterojunction structure nano material
Curve (a) and corresponding Tafel slope (b)；
Fig. 5 is that embodiment 1 prepares the hollow MoS of gained2/MoO3Flower ball-shaped heterojunction structure nano material under acidic electrolysis bath
Current density changes with time figure under 200mV overpotential；
Fig. 6 is that embodiment 1 prepares the hollow MoS of gained2/MoO3The test of flower ball-shaped heterojunction structure nano material photocatalytic activity；
Fig. 7 is that embodiment 3-6 prepares hollow MoS under gained 2h, 6h reaction condition2/MoO3Flower ball-shaped heterojunction structure nano material
Transmission electron microscope picture；
Fig. 8 is that embodiment 7-9 prepares hollow MoS under 120 DEG C of gained, 160 DEG C of reaction conditions2/MoO3Flower ball-shaped heterojunction structure is received
The transmission electron microscope picture of rice material.
Embodiment
Technical scheme is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
In following embodiments, four thio ammonium molybdate（Analysis is pure）Purchased from Sigma-Aldrich trade Co., Ltd, urea
（Analysis is pure）Purchased from Guangdong Province fine chemicals engineering and technological research development centre.
Embodiment 1
A kind of hollow MoS2/MoO3The preparation method of flower ball-shaped heterojunction structure nano material, it comprises the following steps：
1）In 100mL beakers, 22mg four thio ammonium molybdate and 22mg urea are added, 35ml N, N- dimethyl formyls is added
Amine, ultrasound 50min is to form homogeneous solution in ultrasonic cleaner.Then 0.1ml hydrazine hydrates are added, in ultrasonic cleaner
In ultrasound 30min again；
2）By step 1）Resulting solution is moved into 100ml reactors, is put into electric heating constant-temperature blowing drying box and is carried out solvent thermal reaction,
Kept for 200 DEG C, react 10h；
3）After reaction terminates, naturally cool to room temperature, reaction solution is centrifuged, precipitate scrubbed, vacuum drying produce it is hollow
MoS2/MoO3Flower ball-shaped heterojunction structure nano material.
The hollow MoS of gained target product2/MoO3The transmission electron microscope TEM figures of flower ball-shaped heterojunction structure nano material are shown in Fig. 1.X
X-ray photoelectron spectroscopy X figure（XPS）See Fig. 2.X-ray diffraction spectrogram（XRD）And Raman spectrum（Raman spectra）See in Fig. 3
A, b.The a that polarization curve for electrochemistry evolving hydrogen reaction is shown in Fig. 4, the b that corresponding Tafel slope is shown in Fig. 4.For
In terms of electrocatalytic hydrogen evolution, the change with time catalytic activity of figure of current density is shown in Fig. 5 under 200mV overpotential.For photocatalysis
Catalytic activity in terms of liberation of hydrogen is shown in Fig. 6.The transmission electron microscope TEM figures of the product of differential responses time are shown in Fig. 7, and different reaction temperatures
The TEM figures of product see Fig. 8.
Above-mentioned characterization result shows：Four thio ammonium molybdate is used for raw material, under the conditions of solvent thermal reaction, is obtained hollow
MoS2/MoO3Hetero nano structure, the appearance structure with flower ball-shaped, inner hollow, petal be assembled by a series of nanometer sheets and
Into（See Fig. 1）.X-ray diffraction（XRD）Collection of illustrative plates（Fig. 3 a）Prove there is MoS in flower ball-shaped nanometer framework2（JCPDS No.37-
1492）And MoO3（JCPDS No.89-5108）.With MoS2And MoO3XRD standard cards compare, deposited in the XRD spectrum of sample
In MoS2Strong diffraction maximum and MoO3Weak diffraction maximum, show to contain MoS in bouquet2And MoO3。MoO3Presence can make MoS2Tool
There are more sites for being rich in defect.Raman spectrum（Fig. 3 b）In, in 142,212 and 375cm-1The characteristic peak at place represents 1T-
MoS2.By contrast, 110,126,197,238,285 and 332cm-1The characteristic peak at place shows in 1T-MoS2Have one in main body
Quantitative MoO3.Adulterate MoO3MoS2Material can make MoS2More avtive spots are obtained, and then improve the performance of material.
The hollow MoS of product of preparation2/MoO3Flower ball-shaped heterojunction structure nano material is loaded on glass-carbon electrode with three electricity
Polar body system test performance, electrolyte is 0.5 M H2SO4.For HER, hollow MoS2/MoO3Flower ball-shaped nanometer framework is shown
110mV small overpotential, more than the value, cathode current rises rapidly（Fig. 4 a）.It is small compared to the nano material of other structures
Overpotential causes material of the present invention to have more advantage in actual applications.
As control, the present invention also measures calcining prepared by the MoS nanometer sheets of the preparation of reference examples 1, embodiment 2
MoS2/MoO3Nano material product, their take-off potential is respectively 106mV and 73mV, shows poor HER activity.This hair
Bright hollow MoS2/MoO3Flower ball-shaped heterojunction structure nano material, which has, is much smaller than highly crystalline sample（160-250mV）It is excessively electric
Gesture, shows that this nano material has good catalytic activity.In order to further appreciate that hollow MoS of the invention2/MoO3Flower ball-shaped
The Hydrogen Evolution Performance of nano material, the application have studied the Tafel curve figure of various catalyst（Fig. 4 b）.Wherein, the present invention is hollow
MoS2/MoO3The slope of the Tafel curve of flower ball-shaped nano material is 42mV/dec, and its numerical value is less than many bases so far
In MoS2HER catalyst, but embodiment 2 prepare calcining MoS2/MoO3Nano material product, MoS nanometer sheets and business
MoS2Then there is higher Tafel slope, the mV/dec of respectively 73,106 and 186.The trourelle Fei Er of this nano material is oblique
Rate is favourable for practical application.Because with the increase of overpotential, it will cause HER speed faster to increase.
In order to explore hollow MoS of the invention2/MoO3Durability of the flower ball-shaped heterojunction structure nano material in sour environment,
The application has carried out the long-term cyclic test of static overpotential（Fig. 5）.When applying 200mV overpotential, connect in HER
It is continuous to produce H2Molecular process.In Figure 5, there is typical zigzag fashion, this is due to the alternating that bubble accumulation and bubble discharge
Process.Current density also only shows slight slip after the long-time of 11000 seconds, and this is probably due to H+Subtract
Less or H2The covering electrode surface of bubble is hindered caused by reaction.In this work the durability that obtains than report before its
He is MoS2The nano material of support is more preferable.It shows good long-term cycle performance, to provide extremely strong electrochemical stability.
In order to test influence of the photocatalysis to structure, hollow MoS2/MoO3The H of nanometer globe daisy2The time course of release is as shown in Figure 6.This
Plant catalyst and possess almost 22 mmol g-1 h-1H2, than business MoS2It is high 27 times.Preliminary surveying shows, hollow MoS2/MoO3
Globular flower shows more preferable photocatalytic activity.
Reference examples 1
A kind of preparation method of MoS nanometer sheets, it comprises the following steps：
1）By four thio ammonium molybdate and urea（Mass ratio 1：1）It is added in DMF：Other steps 1 of step be the same as Example 1）；
2）Solvent thermal reaction：The step 2 of be the same as Example 1）；
3）Washing, dry, collection product, the step 3 of be the same as Example 1）.
Hydrazine hydrate direct solvent thermal response MoS nanometer sheet electro-chemical test figures are not added with to see in Fig. 4（a）, can see in figure
Go out：Compared with embodiment 1, overpotential is substantially bigger than embodiment 1 and its cathode-current density is significantly smaller.It is possible thereby to
Go out：Add after hydrazine hydrate processing, significantly improve electrochemistry Hydrogen Evolution Performance.
Embodiment 2
A kind of MoS of calcining2/MoO3The preparation method of nano material, it comprises the following steps：
1）Four thio ammonium molybdate, urea, hydrazine hydrate are added in DMF：The step 1 of be the same as Example 1）；
2）Solvent thermal reaction：The step 2 of be the same as Example 1）；
3）Washing, dry, collection product, the step 3 of be the same as Example 1）.
4）Be carbonized 2h at 350 DEG C, naturally cools to room temperature, and the black powder of acquisition produces the MoS of calcining2/MoO3Nanometer material
Material.
Embodiment 3-6
A kind of hollow MoS2/MoO3The preparation method of flower ball-shaped heterojunction structure nano material, it comprises the following steps：
1）Four thio ammonium molybdate, urea, hydrazine hydrate are added in DMF：The step 1 of be the same as Example 1）；
2）Solvent thermal reaction, difference be the reaction time be respectively 2,4,6,8h：Other steps 2 of step be the same as Example 1）；
Washing, dry, collection product, the step 3 of be the same as Example 1）.
Embodiment 3 to 6 prepares the hollow MoS of gained2/MoO3The transmission electron microscope TEM figures of flower ball-shaped heterojunction structure nano material are such as
Shown in Fig. 7.First stage, in 2 h, solid MoS is grown2/MoO3Globe daisy, product does not possess cavity structure（A in Fig. 7）.
With the increase in reaction time, after 6 h are reacted, globe daisy gradually forms cavity structure, and in subsequent reaction cavity structure
Become larger and further form hollow MoS2/MoO3Globe daisy.Until reacting after 10 h, product cavity reaches maximum.And with when
Between increase, the nanometer sheet on globe daisy is also from intensive to gradually spreading out, beneficial to the contact area increased in catalytic process.
Embodiment 7-9
A kind of hollow MoS2/MoO3The preparation method of flower ball-shaped heterojunction structure nano material, it comprises the following steps：
1）Four thio ammonium molybdate, urea, hydrazine hydrate are added in DMF：The step 1 of be the same as Example 1）；
2）Solvent thermal reaction, difference is that reaction temperature is respectively 120 DEG C, 160 DEG C, 240 DEG C：Other steps of step be the same as Example 1
Rapid 2）；
3）Washing, dry, collection product, the step 3 of be the same as Example 1）.
Embodiment 7 to 9 prepares the hollow MoS of gained2/MoO3The transmission electron microscope TEM figures of flower ball-shaped heterojunction structure nano material are such as
Shown in Fig. 8.TEM image shows evolution process of the nanostructured with temperature.First medicine ball is formed under conditions of 120 DEG C
Shape, then gradually forms hollow MoS by improving reaction temperature2/MoO3Nanometer globe daisy.
Claims (6)
1. a kind of preparation method of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material, it is characterised in that bag
Include following steps：
1）Four thio ammonium molybdate, urea and hydrazine hydrate are scattered in N,N-dimethylformamide to form homogeneous solution；
2）By step 1）Resulting solution moves into reactor, and 8-10h is reacted in 160-240 DEG C；
3）After reaction terminates, naturally cool to room temperature, separation of solid and liquid, precipitate it is scrubbed, be drying to obtain hollow MoS2/MoO3Bouquet
Shape heterojunction structure nano material.
2. the preparation method of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material as claimed in claim 1, its
It is characterised by, step 1）In, the mass ratio of four thio ammonium molybdate and urea is 1：1-1.5；Four thio ammonium molybdate per 22mg is added
0.05-0.2ml hydrazine hydrate.
3. the preparation method of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material as claimed in claim 1, its
It is characterised by, step 2）During middle reaction, reaction temperature is 200 DEG C, and the reaction time is 10h.
4. the preparation method of hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material as claimed in claim 1, its
It is characterised by, step 3）In, separation of solid and liquid is from centrifuging, and centrifugal rotational speed is that 9000-10000 rpm, centrifugation time are
5-10 min.
5. hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped hetero-junctions obtained by being prepared using any methods described of Claims 1-4
Structure nano material.
6. hollow molybdenum disulfide/molybdenum trioxide flower ball-shaped heterojunction structure nano material described in claim 5 is improving catalyst
Application in terms of Hydrogen Evolution Performance.
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| CN108671944A (en) * | 2018-05-29 | 2018-10-19 | 武汉工程大学 | A kind of nickel molybdenum oxide@nickel molybdenum sulphide@nickel foam composite nano materials and the preparation method and application thereof |
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| CN109650448A (en) * | 2018-12-29 | 2019-04-19 | 广西大学 | A kind of α-MoO3The preparation method of nano-hollow ball |
| 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 |
| CN110106519A (en) * | 2019-06-20 | 2019-08-09 | 温州大学 | TiO2/MoS2The preparation method of ultrathin nanometer chip arrays composite material |
| CN111111729A (en) * | 2019-12-18 | 2020-05-08 | 西安交通大学 | Molybdenum disulfide-based nanocomposite material with hollow sandwich laminated structure and preparation method thereof |
| CN112899720A (en) * | 2021-01-15 | 2021-06-04 | 华中科技大学 | Mo/MoO with ampere-level current density hydrogen evolution performance2Preparation of in-plane heterojunctions |
| 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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