CN107344099B - A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst - Google Patents
A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst Download PDFInfo
- Publication number
- CN107344099B CN107344099B CN201710527065.5A CN201710527065A CN107344099B CN 107344099 B CN107344099 B CN 107344099B CN 201710527065 A CN201710527065 A CN 201710527065A CN 107344099 B CN107344099 B CN 107344099B
- Authority
- CN
- China
- Prior art keywords
- moo
- mos
- preparation
- catalyst
- eda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 30
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 30
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 9
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000000386 microscopy Methods 0.000 description 4
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B01J35/33—
Abstract
The invention discloses a kind of one-dimentional structure MoO2‑MoS2The preparation method of elctro-catalyst, comprising the following steps: (1) it is ammonium molybdate and ethylenediamine is according to the molar ratio of 1:10 soluble in water, pH to 4~5 is adjusted, reaction 2h obtains MoO at 50 DEG C3-EDA；(2) under an ar atmosphere to MoO3- EDA carries out calcination, and calcination 5h at 650 DEG C obtains MoO2；(3) by MoO2It is added to the water with thioacetamide according to the molar ratio of 1:5,200 DEG C of reactions obtain MoO in closed reactor2‑MoS2；(4) temperature is cooled to room temperature separation solid, washs drying.The invention has the beneficial effects that: (1) reaction temperature low, simple process is controllable, environmental-friendly, and yield is big, reproducible, product morphology is uniform, is very suitable to be mass produced；(2) process reacted by simple adjustment, can prepare the MoO with different activities2‑MoS2Elctro-catalyst.
Description
Technical field
The present invention relates to a kind of preparation methods of elctro-catalyst, and in particular to a kind of one-dimentional structure MoO2-MoS2Electro-catalysis
The preparation method of agent belongs to inorganic material and functional material fabricating technology field.
Background technique
With the development of human society, conventional fossil fuel bring energy crisis and environmental problem are more serious,
Searching more cleaning, environmental protection, sustainable new energy are just particularly important.Hydrogen Energy (H2) again environmentally friendly as a kind of not only high energy
New energy has obtained the extensive concern of people.And obtaining the most direct mode of hydrogen is exactly electrolysis water.The mankind have found at present
Most efficient electrolysis water catalyst be platinum, but because the lower abundance of platinum and high cost make it be difficult to promote and make
With.Therefore, finding non-precious metal catalyst efficiently, economic, environmentally friendly just becomes the emphasis of everybody concern.
MoO2Rutile structure with distortion is a typical transition metal oxide. MoO2With high chemistry
Stability and lesser resistance coefficient are the catalyst with research and development potentiality.But pure MoO2Catalytic
Can be general, so research MoO2Mutually compound material is just at the direction broken through with other substances.
Currently, having been reported that by growing MoO in nickel foam2Catalyst is prepared, also by MoO2It is electrodeposited on carbon and makes
Make catalyst.Although these method simple possibles, if being mass produced if necessary, because cost and technique
Reason is not easy to realize.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of one-dimentional structure MoO2-MoS2Electro-catalysis
The preparation method of agent, the preparation method yield is big, reproducible, simple process, environmental-friendly, and can pass through simple adjustment
The process of reaction prepares the elctro-catalyst of different activities.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst, which comprises the following steps:
Step1: ammonium molybdate and ethylenediamine are dissolved in suitable quantity of water according to the molar ratio of 1:10, with the salt acid for adjusting pH of 1M
To 4~5,2h is then reacted at 50 DEG C and obtains MoO3-EDA；
Step2: under an ar atmosphere to MoO3- EDA carries out calcination, and calcination 5h at 650 DEG C obtains MoO2；
Step3: by MoO2It is added in suitable quantity of water with thioacetamide according to the molar ratio of 1:5, stirs simultaneously ultrasonic disperse,
It is added in closed reactor later, reaction obtains MoO at 200 DEG C2-MoS2；
Step4: reaction temperature is cooled to room temperature separation solid, washs drying.
Preparation method above-mentioned, which is characterized in that in Step2, when calcination, heating rate is 5 DEG C/min.
Preparation method above-mentioned, which is characterized in that in Step3, the time of ultrasonic disperse is 30min.
Preparation method above-mentioned, which is characterized in that in Step3, reaction time 3h, 6h or 12h.
Preparation method above-mentioned, which is characterized in that in Step4, product deionized water and ethanol washing will wash
Product afterwards is placed on freeze-day with constant temperature in 50 DEG C of baking ovens and stays overnight.
The invention has the beneficial effects that:
(1) not only reaction temperature is low, simple process is controllable, environmental-friendly for preparation method of the invention (solvent-thermal method), and
And yield is big, reproducible, product morphology is uniform, is very suitable to be mass produced.
(2) process reacted by simple adjustment Step3 can prepare the MoO with different activities2-MoS2Electro-catalysis
Agent.
Detailed description of the invention
Fig. 1 (a) is the MoO obtained after (Step2) calcination2Scanning electron microscope photo；
Fig. 1 (b) to Fig. 1 (d) is by differential responses time MoO obtained2-MoS2Scanning electron microscope photograph
Piece；
Fig. 2 (a) to Fig. 2 (c) is the MoO obtained of embodiment 32-MoS2Transmission microscopy photo, wherein Fig. 2 (c)
It is high-resolution transmission microscopy photo；
Fig. 3 (a) is MoO2And use different hydro-thermal time obtained MoO2-MoS2The XRD diagram of elctro-catalyst；
Fig. 3 (b) is XRD diagram of the sample of hydro-thermal 12h after different temperatures is annealed；
Fig. 4 (a) to Fig. 4 (d) is the MoO obtained of embodiment 32-MoS2XPS figure, wherein Fig. 4 (a) is score,
Fig. 4 (b) is the peak figure of Mo 3d, and Fig. 4 (c) is the peak figure of S 2p, and Fig. 4 (d) is the peak figure of O 1s；
Fig. 5 (a) and Fig. 5 (b) is MoO respectively2And MoO2-MoS2The specific surface area test chart of (3h, 6h, 12h) and aperture
Distribution map；
Fig. 6 (a) to Fig. 6 (d) is the electrocatalysis characteristic test chart of sample, wherein Fig. 6 (a) is polarization curve, Fig. 6
It (b) is Tafel curve figure, Fig. 6 (c) is testing impedance figure, and Fig. 6 (d) is the cyclical stability figure of 12h sample and 1000
Circulation front and back polarization curve variation diagram.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
Step1: synthesis MoO3-EDA
By 1.24kg ammonium molybdate ((NH4)6Mo7O24·4H2O it) is dissolved in 15L deionized water, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the molar ratio of ammonium molybdate and ethylenediamine is 1:10, the hydrochloric acid that then addition concentration is 1M while stirring, with
After have white precipitate generation, continue to be added dropwise HCl until the pH of solution reaches 4, react the production that 2h obtains white at 50 DEG C later
Then object filters the product of the white, and is washed with deionized water and ethyl alcohol, finally put the product of the white
It sets the dry 10h in 50 DEG C of baking oven and obtains MoO3-EDA。
Step2: preparation MoO2
Take MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, heating rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, obtains MoO after being cooled to room temperature2。
Step3: synthesis MoO2-MoS2
Take the MoO of club shaped structure prepared by 50g Step22With 150g thioacetamide (TAA), the molar ratio of the two
For 1:5, the two is added in 30L deionized water simultaneously, 25min, re-ultrasonic dispersion 30min is first stirred, later turns solution
Move on to closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining lining, 3h is reacted at 200 DEG C, obtains rodlike knot
The MoO of structure2-MoS2。
Step4: post-processing
Be cooled to room temperature to reaction temperature, separate solid product, and use deionized water and ethanol washing, finally will wash after
Solid be placed into 50 DEG C of baking oven dry overnight.
Embodiment 2
Step1: synthesis MoO3-EDA
By 1.24kg ammonium molybdate ((NH4)6Mo7O24·4H2O it) is dissolved in 15L deionized water, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the molar ratio of ammonium molybdate and ethylenediamine is 1:10, the hydrochloric acid that then addition concentration is 1M while stirring, with
After have white precipitate generation, continue to be added dropwise HCl until the pH of solution reaches 4, react the production that 2h obtains white at 50 DEG C later
Then object filters the product of the white, and is washed with deionized water and ethyl alcohol, finally put the product of the white
It sets the dry 10h in 50 DEG C of baking oven and obtains MoO3-EDA。
Step2: preparation MoO2
Take MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, heating rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, the MoO of club shaped structure is obtained after being cooled to room temperature2。
Step3: synthesis MoO2-MoS2
Take the MoO of club shaped structure prepared by 50g Step22With 150g thioacetamide (TAA), the molar ratio of the two
For 1:5, the two is added in 30L deionized water simultaneously, 25min, re-ultrasonic dispersion 30min is first stirred, later turns solution
Move on to closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining lining, 6h is reacted at 200 DEG C, obtains rodlike knot
The MoO of structure2-MoS2。
Step4: post-processing
Be cooled to room temperature to reaction temperature, separate solid product, and use deionized water and ethanol washing, finally will wash after
Solid be placed into 50 DEG C of baking oven dry overnight.
Embodiment 3
Step1: synthesis MoO3-EDA
By 1.24kg ammonium molybdate ((NH4)6Mo7O24·4H2O it) is dissolved in 15L deionized water, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the molar ratio of ammonium molybdate and ethylenediamine is 1:10, the hydrochloric acid that then addition concentration is 1M while stirring, with
After have white precipitate generation, continue to be added dropwise HCl until the pH of solution reaches 4, react the production that 2h obtains white at 50 DEG C later
Then object filters the product of the white, and is washed with deionized water and ethyl alcohol, finally put the product of the white
It sets the dry 10h in 50 DEG C of baking oven and obtains MoO3-EDA。
Step2: preparation MoO2
Take MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, heating rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, the MoO of club shaped structure is obtained after being cooled to room temperature2。
Step3: synthesis MoO2-MoS2
Take the MoO of club shaped structure prepared by 50g Step22With 150g thioacetamide (TAA), the molar ratio of the two
For 1:5, the two is added in 30L deionized water simultaneously, 25min, re-ultrasonic dispersion 30min is first stirred, later turns solution
Move on to closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining lining, 12h is reacted at 200 DEG C, obtains rodlike knot
The MoO of structure2-MoS2。
Step4: post-processing
Be cooled to room temperature to reaction temperature, separate solid product, and use deionized water and ethanol washing, finally will wash after
Solid be placed into 50 DEG C of baking oven dry overnight.
Fig. 1 (a) is the MoO obtained after (Step2) calcination2Scanning electron microscope photo；Fig. 1 (b), figure
1 (c) and Fig. 1 (d) is by (Step3) differential responses time MoO obtained respectively2-MoS2Scanning electron microscope photograph
Piece.
By Fig. 1 (a) to Fig. 1 (d) it can be seen that by adjusting (Step3) reaction time, a series of surface hairs can be obtained
The raw MoO with club shaped structure centainly changed2-MoS2Elctro-catalyst.
Fig. 2 (a) to Fig. 2 (c) is the MoO obtained of embodiment 32-MoS2Transmission microscopy photo, wherein Fig. 2 (c)
It is high-resolution transmission microscopy photo.
By Fig. 2 (a) to Fig. 2 (c) it can be seen that the MoO of club shaped structure2-MoS2The inside of elctro-catalyst shows porous knot
Structure.
Fig. 3 (a) is MoO2And use obtained rodlike MoO of different hydro-thermal times2-MoS2The XRD diagram of elctro-catalyst；Fig. 3
It (b) is XRD diagram of the sample of hydro-thermal 12h after different temperatures is annealed.
By Fig. 3 (a) it can be seen that MoO2Crystallinity it is fine.
By Fig. 3 (b) it can be seen that there is apparent MoS when annealing temperature reaches 800 DEG C or more2Peak, this says
Bright sulphur and MoO2By successfully having been combined after water-heat process.
Fig. 4 (a) to Fig. 4 (d) is the MoO obtained of embodiment 32-MoS2XPS figure, wherein Fig. 4 (a) is score,
Fig. 4 (b) is the peak figure of Mo 3d, and Fig. 4 (c) is the peak figure of S 2p, and Fig. 4 (d) is the peak figure of O 1s.
By Fig. 4 (a) it can be seen that containing Mo, O and S element in sample.
By Fig. 4 (b) it can be seen that the position of the peak 229.0eV and 232.3eV of Mo 3d corresponds respectively to Mo4+3d5/2 and
Mo4+3d3/2。
By Fig. 4 (c) it can be seen that the peak 163.3eV and 161.6eV of S 2p have respectively corresponded S 2p1/2 and S 2p3/2.
By Fig. 4 (d) it can be seen that the peak combination of O 1s can be in 530.7eV.
Fig. 5 (a) is MoO2And MoO2-MoS2The specific surface area test chart of (3h, 6h, 12h)；Fig. 5 (b) is MoO2And MoO2-
MoS2The graph of pore diameter distribution of (3h, 6h, 12h).
By Fig. 5 (a) and Fig. 5 (b) it can be seen that by after hydro-thermal process, the specific surface area of sample is greatly improved,
Pore-size distribution is also changed simultaneously.
Fig. 6 (a) to Fig. 6 (d) is the electrocatalysis characteristic test chart of sample, and entire test process uses three-electrode system
(glass-carbon electrode is working electrode, and platinum electrode is to electrode, and Ag/AgCl electrode is as reference electrode), in the H of 1M2SO4Solution
In, it carries out at room temperature, in which:
Fig. 6 (a) is polarization curve (having carried out iR correction), and as can be seen from the figure the sample of hydro-thermal 12h has smaller
Overpotential, and in the case where voltage is the voltage of 210mV, the current density of the sample of hydro-thermal 12h reaches 10mA/cm2, it is higher than it
Sample obtained under the conditions of him；
Fig. 6 (b) is Tafel curve figure, as can be seen from the figure the minimum 51.6mV/ of the Tafel slope of the sample of 12h
dec；
Fig. 6 (c) is testing impedance figure, and as can be seen from the figure the sample of 12h shows smaller impedance, good to lead
It is electrically also that it has the reason of better catalytic performance；
Fig. 6 (d) is the cyclical stability figure and 1000 circulations front and back polarization curve variation diagrams of 12h sample, Cong Tuzhong
It can be seen that polarization curve varies less after 1000 CV, in the survey of fixed voltage (200mV) test current density change
It can be seen that, by the circulating current density of 10h substantially without significant change, about 6mA/cm is maintained in examination2, this is illustrated
The catalytic stability of material is fine.
It can be seen that the elctro-catalyst that (solvent-thermal method) is prepared by means of the present invention, inside configuration have
Porous, specific surface area is improved, and pore-size distribution is changed, and current density reaches 10mA/cm2, Tafel slope minimum
For 51.6mV/dec, there is good electric conductivity and catalytic stability.
In conclusion not only reaction temperature is low, simple process is controllable, environment is friendly for preparation method (solvent-thermal method) of the invention
It is good, and yield is big, reproducible, product morphology is uniform, is very suitable to be mass produced.
In addition, the process that preparation method (solvent-thermal method) of the invention is reacted by simple adjustment Step3, can prepare and provide
There is the MoO of different activities2-MoS2Elctro-catalyst.
It should be noted that the above embodiments do not limit the invention in any form, it is all to use equivalent replacement or equivalent change
The mode changed technical solution obtained, falls within the scope of protection of the present invention.
Claims (5)
1. a kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst, which comprises the following steps:
Step1: ammonium molybdate and ethylenediamine are dissolved in suitable quantity of water according to the molar ratio of 1:10, with the salt acid for adjusting pH of 1M to 4~
5,2h is then reacted at 50 DEG C obtains MoO3-EDA；
Step2: under an ar atmosphere to MoO3- EDA carries out calcination, and calcination 5h at 650 DEG C obtains MoO2；
Step3: by MoO2It is added in suitable quantity of water with thioacetamide according to the molar ratio of 1:5, stirs simultaneously ultrasonic disperse, later
It is added in closed reactor, reaction obtains MoO at 200 DEG C2-MoS2；
Step4: reaction temperature is cooled to room temperature separation solid, washs drying.
2. preparation method according to claim 1, which is characterized in that in Step2, when calcination, heating rate is 5 DEG C/
min。
3. preparation method according to claim 1, which is characterized in that in Step3, the time of ultrasonic disperse is 30min.
4. preparation method according to claim 1, which is characterized in that in Step3, reaction time 3h, 6h or 12h.
5. preparation method according to claim 1, which is characterized in that in Step4, by product deionized water and ethyl alcohol
Washing, is placed on freeze-day with constant temperature in 50 DEG C of baking ovens for the product after washing and stays overnight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710527065.5A CN107344099B (en) | 2017-06-30 | 2017-06-30 | A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710527065.5A CN107344099B (en) | 2017-06-30 | 2017-06-30 | A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107344099A CN107344099A (en) | 2017-11-14 |
| CN107344099B true CN107344099B (en) | 2019-04-05 |
Family
ID=60256624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710527065.5A Expired - Fee Related CN107344099B (en) | 2017-06-30 | 2017-06-30 | A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107344099B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108671944B (en) * | 2018-05-29 | 2021-07-13 | 武汉工程大学 | Nickel-molybdenum oxide @ nickel-molybdenum sulfide @ foamed nickel composite nano material and preparation method and application thereof |
| CN112563522A (en) * | 2020-12-11 | 2021-03-26 | 西北大学 | Preparation method and application of cobalt-doped molybdenum dioxide electrocatalyst |
| CN113430568B (en) * | 2021-07-13 | 2022-08-02 | 西北大学 | Platinum-loaded molybdenum dioxide hybrid nano material, preparation method and electrocatalysis application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367713A (en) * | 2013-08-05 | 2013-10-23 | 黑龙江大学 | Preparation method for MoO2/MoS2 composite nanorod |
| CN105514403A (en) * | 2016-01-13 | 2016-04-20 | 陕西科技大学 | Three-dimensional core-shell structure MoO2-MoS2 lithium ion battery cathode material and preparing method thereof |
| CN106410150A (en) * | 2016-11-04 | 2017-02-15 | 陕西科技大学 | MoO2-MoS2 negative electrode material of sodium-ion battery with core-shell structure and preparation method of MoO2-MoS2 negative electrode material |
-
2017
- 2017-06-30 CN CN201710527065.5A patent/CN107344099B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367713A (en) * | 2013-08-05 | 2013-10-23 | 黑龙江大学 | Preparation method for MoO2/MoS2 composite nanorod |
| CN105514403A (en) * | 2016-01-13 | 2016-04-20 | 陕西科技大学 | Three-dimensional core-shell structure MoO2-MoS2 lithium ion battery cathode material and preparing method thereof |
| CN106410150A (en) * | 2016-11-04 | 2017-02-15 | 陕西科技大学 | MoO2-MoS2 negative electrode material of sodium-ion battery with core-shell structure and preparation method of MoO2-MoS2 negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction;Linjing Yang et al.,;《Nanoscale》;20150210;第7卷;5203-5208 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107344099A (en) | 2017-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109252180B (en) | Ternary MOF nanosheet array material, preparation method and application thereof | |
| CN108118362B (en) | Molybdenum disulfide electrocatalytic hydrogen production electrode and preparation method and application thereof | |
| CN109201060B (en) | Preparation method of foamed nickel-nickel iron oxide composite oxygen evolution catalyst | |
| CN109516505B (en) | Preparation method of cobalt sulfide, product and application thereof | |
| CN108325539B (en) | Rod-like vanadium modified Ni self-assembled into flower ball shape3S2Synthesis method of electrocatalyst | |
| CN109225270B (en) | Ni3S2@ NiV-LDH heterostructure bifunctional electrocatalyst, preparation method and application | |
| CN108425131B (en) | Nickel-molybdenum-based alloy loaded on foamed nickel, amorphous carbon system, and preparation method and application thereof | |
| CN108671923B (en) | Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof | |
| CN105289614B (en) | A kind of preparation method of nickel carbon-supported catalysts material for hydrogen manufacturing | |
| CN110433833B (en) | Non-noble metal hydrogen evolution electrocatalyst based on synergistic modification and preparation method thereof | |
| CN107344099B (en) | A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst | |
| CN109621981B (en) | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN109304187B (en) | Hollow nano composite material, preparation method and application thereof | |
| CN109908905B (en) | Method for preparing metal/metal oxide composite electrocatalyst | |
| CN110965076A (en) | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure | |
| CN109455774A (en) | A kind of Ni-Fe-OH/MoS2/Ni3S2Composite nano plate/carbon cloth, preparation method and application | |
| CN109371419B (en) | V-doped Ni with self-assembled short rods into dendritic shape3S2/NF electrode material and preparation method thereof | |
| CN108977849B (en) | MXene/Ni3S2Electrode, preparation method thereof and application thereof in preparing hydrogen by electrocatalysis | |
| CN109133199A (en) | A kind of preparation method of the spherical nanometer molybdic acid nickel electrode material of high circulation performance | |
| CN111715245A (en) | Based on high catalytic activity and crystalline RuTe2The electrolytic water catalyst and the preparation method thereof | |
| CN113818041B (en) | Heterostructure material of ultrathin bimetal molybdate nanosheet coated nanotube, and preparation method and application thereof | |
| CN112553643B (en) | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application | |
| CN112899723B (en) | Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof | |
| CN113355682A (en) | Iron-doped trifluoro cobaltate oxygen evolution electro-catalytic material, preparation method and application thereof | |
| CN110230072B (en) | Preparation method and application of N-NiZnCu LDH/rGO nanosheet array material on foamed nickel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190405 Termination date: 20210630 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |