CN107344099A - 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
- CN107344099A CN107344099A CN201710527065.5A CN201710527065A CN107344099A CN 107344099 A CN107344099 A CN 107344099A CN 201710527065 A CN201710527065 A CN 201710527065A CN 107344099 A CN107344099 A CN 107344099A
- Authority
- CN
- China
- Prior art keywords
- moo
- mos
- preparation
- catalyst
- elctro
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 31
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 31
- 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 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 6
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000463 material Substances 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
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 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
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 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
- 238000006467 substitution reaction Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of one-dimentional structure MoO2‑MoS2The preparation method of elctro-catalyst, comprises the following steps：(1) by ammonium molybdate and ethylenediamine according to 1：10 mol ratio is soluble in water, adjusts pH to 4~5, and reacting 2h at 50 DEG C obtains MoO3‑EDA；(2) under an ar atmosphere to MoO3EDA carries out calcination, calcination 5h at 650 DEG C, obtains MoO2；(3) by MoO2With thioacetamide according to 1：5 mol ratio is added to the water, 200 DEG C of reaction acquisition MoO in closed reactor2‑MoS2；(4) temperature separates solid after being down to room temperature, washs drying.The present invention is advantageous in that：(1) reaction temperature is low, technique is simple controllable, environment-friendly, and yield is big, reproducible, product morphology is homogeneous, is especially suitable for being 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 method of elctro-catalyst, and in particular to a kind of one-dimentional structure MoO2-MoS2Elctro-catalyst
Preparation method, belong to inorganic material and functional material fabricating technology field.
Background technology
With the development of human society, the energy crisis and environmental problem that conventional fossil fuel is brought are more serious,
Searching is more cleaned, is environmentally friendly, sustainable new energy is just particularly important.Hydrogen Energy (H2) as a kind of not only high energy but environmental protection
New energy has obtained the extensive concern of people.And it is exactly electrolysis water to obtain the most direct mode of hydrogen.The mankind have found at present
Most efficient electrolysis water catalyst be platinum, but because the relatively low abundance of platinum and high cost make it that it is difficult that popularization makes
With.Therefore, the non-precious metal catalyst found efficiently, economic, environmentally friendly just turns into the emphasis that everybody pays close attention to.
MoO2Rutile structure with distortion, it is a typical transition metal oxide.MoO2It is steady with high chemistry
Qualitative and less resistance coefficient, it is a catalyst with research and development potentiality.But pure MoO2Catalytic performance
Typically, so research MoO2Mutually compound material is just into the direction broken through with other materials.
At present, have been reported that by growing MoO in nickel foam2Catalyst is prepared, also by MoO2It is electrodeposited on carbon and makes
Catalyst.Although these method simple possibles, if being mass produced if desired, because the original of cost and technique
Cause, it is not easy to realize.
The content of the invention
To solve the deficiencies in the prior art, it is an object of the invention to provide a kind of one-dimentional structure MoO2-MoS2Elctro-catalyst
Preparation method, the preparation method yield is big, reproducible, technique is simple, environment-friendly, and can be anti-by simple adjustment
The process answered prepares the elctro-catalyst of different activities.
In order to realize above-mentioned target, the present invention adopts the following technical scheme that：
A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst, it is characterised in that comprise the following steps：
Step1：By ammonium molybdate and ethylenediamine according to 1：10 mol ratio is dissolved in suitable quantity of water, with 1M salt acid for adjusting pH extremely
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, calcination 5h at 650 DEG C, obtains MoO2；
Step3：By MoO2With thioacetamide according to 1：5 mol ratio is added in suitable quantity of water, stirs simultaneously ultrasonic disperse,
It is added to afterwards in closed reactor, the reaction acquisition MoO at 200 DEG C2-MoS2；
Step4：Reaction temperature separates solid after being down to room temperature, washs drying.
Foregoing preparation method, it is characterised in that in Step2, during calcination, programming rate is 5 DEG C/min.
Foregoing preparation method, it is characterised in that in Step3, the time of ultrasonic disperse is 30min.
Foregoing preparation method, it is characterised in that in Step3, reaction time 3h, 6h or 12h.
Foregoing preparation method, it is characterised in that in Step4, product is washed with deionized water and ethanol, will be washed
Product afterwards is placed on freeze-day with constant temperature in 50 DEG C of baking ovens and stayed overnight.
The present invention is advantageous in that：
(1) not only reaction temperature is low, technique is simple controllable, environment-friendly for preparation method (solvent-thermal method) of the invention, and
And yield is big, reproducible, product morphology is homogeneous, is especially suitable for being mass produced.
(2) process reacted by simple adjustment Step3, the MoO with different activities can be prepared2-MoS2Electro-catalysis
Agent.
Brief description of the drawings
Fig. 1 (a) is the MoO obtained after (Step2) calcination2SEM photo；
Fig. 1 (b) to Fig. 1 (d) is the MoO obtained by the differential responses time2-MoS2SEM photograph
Piece；
Fig. 2 (a) to Fig. 2 (c) is the MoO that embodiment 3 is obtained2-MoS2Transmission microscopy photo, wherein, Fig. 2 (c)
It is high-resolution transmission microscopy photo；
Fig. 3 (a) is MoO2And using the MoO obtained by the different hydro-thermal times2-MoS2The XRD of elctro-catalyst；
Fig. 3 (b) is XRD of the hydro-thermal 12h sample after different temperatures is annealed；
Fig. 4 (a) to Fig. 4 (d) is the MoO that embodiment 3 is obtained2-MoS2XPS figure, wherein, Fig. 4 (a) is score, figure
4 (b) is Mo 3d peak figure, and Fig. 4 (c) is S 2p peak figure, and Fig. 4 (d) is O 1s peak figure；
Fig. 5 (a) and Fig. 5 (b) is MoO respectively2And MoO2-MoS2The specific surface area test chart of (3h, 6h, 12h) and aperture point
Butut；
Fig. 6 (a) to Fig. 6 (d) is the electrocatalysis characteristic test chart of sample, wherein, Fig. 6 (a) is polarization curve, Fig. 6
(b) it is Tafel curve figure, Fig. 6 (c) is testing impedance figure, and Fig. 6 (d) is the cyclical stability figure of 12h samples and 1000
Polarization curve variation diagram before and after circulation.
Embodiment
Make specific introduce to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
Step1：Synthesize MoO3-EDA
By 1.24kg ammonium molybdates ((NH4)6Mo7O24·4H2O) it is dissolved in 15L deionized waters, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the mol ratio of ammonium molybdate and ethylenediamine is 1：10, the hydrochloric acid that concentration is 1M is then added 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 afterwards
Thing, then the product white to this filters, and is washed with deionized water and ethanol, finally puts the white product
Put the dry 10h in 50 DEG C of baking oven and obtain MoO3-EDA。
Step2：Prepare MoO2
Take the MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, programming rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, MoO is obtained after being cooled to room temperature2。
Step3：Synthesize MoO2-MoS2
Take the MoO of the club shaped structure prepared by 50g Step22With 150g thioacetamides (TAA), the mol ratio of the two is
1：5, the two is added in 30L deionized waters simultaneously, 25min, then ultrasonic disperse 30min is first stirred, afterwards shifts solution
To closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining linings, 3h is reacted at 200 DEG C, obtains club shaped structure
MoO2-MoS2。
Step4：Post processing
After question response temperature is down to room temperature, solid product is separated, and is washed with deionized water and ethanol, after finally washing
Solid be placed into 50 DEG C of baking oven dry overnight.
Embodiment 2
Step1：Synthesize MoO3-EDA
By 1.24kg ammonium molybdates ((NH4)6Mo7O24·4H2O) it is dissolved in 15L deionized waters, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the mol ratio of ammonium molybdate and ethylenediamine is 1：10, the hydrochloric acid that concentration is 1M is then added 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 afterwards
Thing, then the product white to this filters, and is washed with deionized water and ethanol, finally puts the white product
Put the dry 10h in 50 DEG C of baking oven and obtain MoO3-EDA。
Step2：Prepare MoO2
Take the MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, programming rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, is cooled to the MoO of acquisition club shaped structure after room temperature2。
Step3：Synthesize MoO2-MoS2
Take the MoO of the club shaped structure prepared by 50g Step22With 150g thioacetamides (TAA), the mol ratio of the two is
1：5, the two is added in 30L deionized waters simultaneously, 25min, then ultrasonic disperse 30min is first stirred, afterwards shifts solution
To closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining linings, 6h is reacted at 200 DEG C, obtains club shaped structure
MoO2-MoS2。
Step4：Post processing
After question response temperature is down to room temperature, solid product is separated, and is washed with deionized water and ethanol, after finally washing
Solid be placed into 50 DEG C of baking oven dry overnight.
Embodiment 3
Step1：Synthesize MoO3-EDA
By 1.24kg ammonium molybdates ((NH4)6Mo7O24·4H2O) it is dissolved in 15L deionized waters, first adds 0.8kg while stirring
Ethylenediamine (C2H8N2), the mol ratio of ammonium molybdate and ethylenediamine is 1：10, the hydrochloric acid that concentration is 1M is then added 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 afterwards
Thing, then the product white to this filters, and is washed with deionized water and ethanol, finally puts the white product
Put the dry 10h in 50 DEG C of baking oven and obtain MoO3-EDA。
Step2：Prepare MoO2
Take the MoO synthesized by 200g Step13- EDA is placed under Ar atmosphere, to MoO3- EDA carries out calcination, programming rate 5
DEG C/min, 5h is kept after being warming up to 650 DEG C, is cooled to the MoO of acquisition club shaped structure after room temperature2。
Step3：Synthesize MoO2-MoS2
Take the MoO of the club shaped structure prepared by 50g Step22With 150g thioacetamides (TAA), the mol ratio of the two is
1：5, the two is added in 30L deionized waters simultaneously, 25min, then ultrasonic disperse 30min is first stirred, afterwards shifts solution
To closed reactor --- in the hydrothermal reaction kettle of 60L polytetrafluoroethyllining linings, 12h is reacted at 200 DEG C, obtains club shaped structure
MoO2-MoS2。
Step4：Post processing
After question response temperature is down to room temperature, solid product is separated, and is washed with deionized water and ethanol, after finally washing
Solid be placed into 50 DEG C of baking oven dry overnight.
Fig. 1 (a) is the MoO obtained after (Step2) calcination2SEM photo；Fig. 1 (b), figure
1 (c) and Fig. 1 (d) are the MoO obtained by (Step3) differential responses time respectively2-MoS2SEM photograph
Piece.
It can be seen that by Fig. 1 (a) to Fig. 1 (d)：By adjusting (Step3) reaction time, a series of surface hairs can be obtained
The raw MoO with club shaped structure necessarily changed2-MoS2Elctro-catalyst.
Fig. 2 (a) to Fig. 2 (c) is the MoO that embodiment 3 is obtained2-MoS2Transmission microscopy photo, wherein, Fig. 2 (c)
It is high-resolution transmission microscopy photo.
It can be seen that by Fig. 2 (a) to Fig. 2 (c)：The MoO of club shaped structure2-MoS2The inside of elctro-catalyst shows porous knot
Structure.
Fig. 3 (a) is MoO2And using the bar-shaped MoO obtained by the different hydro-thermal times2-MoS2The XRD of elctro-catalyst；Fig. 3
(b) it is XRD of the hydro-thermal 12h sample after different temperatures is annealed.
It can be seen that by Fig. 3 (a)：MoO2Crystallinity it is fine.
It can be seen that by Fig. 3 (b)：When annealing temperature reaches more than 800 DEG C, there is obvious MoS2Peak, this says
Bright sulphur and MoO2By successfully having been combined after water-heat process.
Fig. 4 (a) to Fig. 4 (d) is the MoO that embodiment 3 is obtained2-MoS2XPS figure, wherein, Fig. 4 (a) is score, figure
4 (b) is Mo 3d peak figure, and Fig. 4 (c) is S 2p peak figure, and Fig. 4 (d) is O 1s peak figure.
It can be seen that by Fig. 4 (a)：Contain Mo, O and S element in sample.
It can be seen that by Fig. 4 (b)：Mo 3d peak 229.0eV and 232.3eV position correspond respectively to Mo4+3d5/2 and
Mo4+3d3/2。
It can be seen that by Fig. 4 (c)：S 2p peak 163.3eV and 161.6eV has corresponded to S 2p1/2 and S 2p3/2 respectively.
It can be seen that by Fig. 4 (d)：O 1s peak combines 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).
It can be seen that by Fig. 5 (a) and Fig. 5 (b)：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 whole test process uses three-electrode system
(glass-carbon electrode is working electrode, and platinum electrode is that Ag/AgCl electrodes are as reference electrode to electrode), in 1M H2SO4In solution,
Carry out at room temperature, wherein：
Fig. 6 (a) is polarization curve (having carried out iR corrections), and as can be seen from the figure hydro-thermal 12h sample has smaller
Overpotential, and in the case where voltage is 210mV voltage, the current density of hydro-thermal 12h sample reaches 10mA/cm2, higher than other
Under the conditions of obtained sample；
Fig. 6 (b) is Tafel curve figure, as can be seen from the figure the minimum 51.6mV/ of the Tafel slope of 12h sample
dec；
Fig. 6 (c) is testing impedance figure, and as can be seen from the figure 12h sample shows smaller impedance, and good leads
Electrically and it has the reason for more preferable catalytic performance；
Fig. 6 (d) is polarization curve variation diagram before and after the cyclical stability figure of 12h samples and 1000 circulations, from figure
It can be seen that after 1000 CV, polarization curve varies less, in the survey of fixed voltage (200mV) test current density change
It can be seen that, there is no significant change substantially in examination by 10h circulating current density, be maintained at about 6mA/cm2, this is illustrated
The catalytic stability of material is fine.
As can be seen here, the elctro-catalyst being prepared by the method (solvent-thermal method) of the present invention, its 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 summary, not only reaction temperature is low, technique is simply controllable, environment is friendly for preparation method of the invention (solvent-thermal method)
It is good, and yield is big, reproducible, product morphology is homogeneous, is especially suitable for being mass produced.
In addition, the process that the preparation method (solvent-thermal method) of the present 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 invention is not limited in any way for above-described embodiment, it is all to use equivalent substitution or equivalent change
The technical scheme that the mode changed is obtained, all falls within protection scope of the present invention.
Claims (5)
- A kind of 1. one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst, it is characterised in that comprise the following steps：Step1：By ammonium molybdate and ethylenediamine according to 1：10 mol ratio is dissolved in suitable quantity of water, with 1M salt acid for adjusting pH 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, calcination 5h at 650 DEG C, obtains MoO2；Step3：By MoO2With thioacetamide according to 1：5 mol ratio is added in suitable quantity of water, stirs simultaneously ultrasonic disperse, afterwards It is added in closed reactor, the reaction acquisition MoO at 200 DEG C2-MoS2；Step4：Reaction temperature separates solid after being down to room temperature, washs drying.
- 2. preparation method according to claim 1, it is characterised in that in Step2, during calcination, programming rate is 5 DEG C/ min。
- 3. preparation method according to claim 1, it is characterised in that in Step3, the time of ultrasonic disperse is 30min.
- 4. preparation method according to claim 1, it is characterised in that in Step3, reaction time 3h, 6h or 12h.
- 5. preparation method according to claim 1, it is characterised in that in Step4, by product deionized water and ethanol Washing, is placed on freeze-day with constant temperature in 50 DEG C of baking ovens by 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 true CN107344099A (en) | 2017-11-14 |
| CN107344099B 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112563522A (en) * | 2020-12-11 | 2021-03-26 | 西北大学 | Preparation method and application of cobalt-doped molybdenum dioxide electrocatalyst |
| CN113430568A (en) * | 2021-07-13 | 2021-09-24 | 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 |
|---|
| LINJING YANG ET AL.,: "Porous metallic MoO2-supported MoS2 nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction", 《NANOSCALE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113430568A (en) * | 2021-07-13 | 2021-09-24 | 西北大学 | Platinum-loaded molybdenum dioxide hybrid nano material, preparation method and electrocatalysis application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107344099B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108346522B (en) | Cobaltosic oxide hierarchical structure nano array material, preparation method and application thereof | |
| CN109201060B (en) | Preparation method of foamed nickel-nickel iron oxide composite oxygen evolution catalyst | |
| CN109252180B (en) | Ternary MOF nanosheet array material, preparation method and application thereof | |
| CN108325539B (en) | Rod-like vanadium modified Ni self-assembled into flower ball shape3S2Synthesis method of electrocatalyst | |
| CN107151331A (en) | A kind of method of the quick preparation structure controllable metal organic framework compounds of electrochemical method | |
| CN113512731B (en) | Oxygen evolution electrocatalyst, preparation method and application thereof, and water electrolysis device | |
| CN108671923B (en) | Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof | |
| CN109621981B (en) | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof | |
| CN108048868B (en) | Molybdenum nitride nanorod electrode material and preparation method and application thereof | |
| CN111701607A (en) | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof | |
| CN108823591B (en) | Nickel-iron-selenium compound and preparation method and application thereof | |
| CN109437374B (en) | Cobalt-doped copper sulfide nanosheet material rich in defects and sulfur vacancies, and preparation method and application thereof | |
| CN109277104B (en) | Sulfur-rich vanadium-modified NiS2Electrocatalyst and method of making | |
| CN109354056B (en) | Iron-doped copper sulfide nanosheet material with abundant defects and preparation method and application thereof | |
| CN104465117A (en) | ZnCo2O4@MnO core-shell heterostructure nanotube array material, and preparation method and application thereof | |
| CN112080759B (en) | Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea | |
| CN107344099B (en) | A kind of one-dimentional structure MoO2-MoS2The preparation method of elctro-catalyst | |
| CN113818041B (en) | Heterostructure material of ultrathin bimetal molybdate nanosheet coated nanotube, and preparation method and application thereof | |
| CN110449170B (en) | Amorphous MoS2Modified CoS/Co0.85Preparation method of Se heterogeneous nanotube array electrocatalyst | |
| CN114892206A (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN113355682B (en) | Iron-doped trifluoro cobaltate oxygen evolution electrocatalytic material, preparation method and application thereof | |
| CN107117662A (en) | A kind of preparation method of aluminium doping nanometer nickel sulfide floral material | |
| CN112553643B (en) | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application | |
| CN109473634A (en) | Solid phase heat together synthesizes two selenizing molybdenums/N doping carbon-point method | |
| CN115029709B (en) | Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof |
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 |