CN106040264A - Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material - Google Patents
Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material Download PDFInfo
- Publication number
- CN106040264A CN106040264A CN201610459534.XA CN201610459534A CN106040264A CN 106040264 A CN106040264 A CN 106040264A CN 201610459534 A CN201610459534 A CN 201610459534A CN 106040264 A CN106040264 A CN 106040264A
- Authority
- CN
- China
- Prior art keywords
- micron
- hydrogen evolution
- preparation
- molybdenum bisuphide
- hydrogen
- 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.)
- Pending
Links
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
-
- 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
-
- 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
Abstract
The invention discloses a micron molybdenum disulfide hydrogen evolution electro-catalytic material, a preparation method and an application of the micron molybdenum disulfide hydrogen evolution electro-catalytic material in hydrogen evolution electro-catalysis, and belongs to the technical field of catalytic materials. The preparation method comprises the following steps of dissolving ammonium molybdate tetrahydrate (H24Mo7N6O24 4H2O) in a solvent so as to prepare a 0.025-0.05 mol/L of solution; adding thiocarbamide (CH4N2S), wherein the molar ratio of the ammonium molybdate tetrahydrate to the thiocarbamide 1:30 to 1:40; stirring to mix the solution evenly; performing hydrothermal reaction; reducing the temperature to room temperature after the hydrothermal reaction is completed; centrifuging, washing and drying to obtain the micron-grade molybdenum disulfide hydrogen evolution electro-catalytic material. The preparation method disclosed by the invention is low in cost, simple and easily controlled in production process, high in yield, and suitable for industrial production; and the prepared micron sheets are uniform in shape.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to a kind of micron molybdenum bisuphide (MoS2) Electrocatalytic Activity for Hydrogen Evolution Reaction material
Material, preparation method and the application in Electrocatalytic Activity for Hydrogen Evolution Reaction thereof.
Background technology
As a kind of magnesium-yttrium-transition metal disulphide, the molybdenum bisuphide semi-conducting material of layer structure, have good light,
Electricity, lubricate, the performance such as catalysis.The inside of platelike molybdenumdisulfide structure micron film and the atomic bonding-valence at edge are different, internal
Atom be saturated, and the atom at edge is undersaturated, forms dangling bonds, i.e. edge active position Mo-S faceted pebble.Mo-S rib
Face is the most, catalytic performance aspect will have that specific surface area is big, high adsorption capacity, reactivity advantages of higher (Wei Ronghui, nanometer
The preparation of molybdenum bisuphide and physicochemical property research [D] thereof. Jilin University, 2008.05).Research has been reported that MoS more2Preparation:
Climax molybdenum company MoS2The technological process of production is first by the roasting 2h at 650 DEG C of the molybdenite concentrate containing Mo >=56%, fills
Compose the pyrite existed in molybdenum concntrate after nitrogen roasting and be converted into magnetic iron ore.Magnetic iron ore after roasting is prone to by sulfuric acid leaching.
The synthesis MoS such as Russia Sazanov.N.P2Method be pyrolysis molybdenum trisulfide and thio molybdenum acid sodium mixture, will 1:1.2
The molybdenum trisulfide of (quality) and thio molybdenum acid sodium are pyrolyzed about 2 hours at a temperature of 500～635 DEG C, obtain MoS after cooling2Product.
The MoS of output2Purity is high, little [the Sazanov N P.Preparation Method for Molybdenum of mean diameter
Disulfide [P] .RU2156318,2000-09-20].
On the other hand, due to advantages such as combustion heat value are high, combustion product (water) non-environmental-pollution, having that hydrogen is well recognized as is uncommon
Hope and become one of clean energy resource that the following mankind are used, but effectively producing of hydrogen is to limit the wide variety of bottle of hydrogen
Neck.At present the method for hydrogen making is a lot, and wherein water electrolysis hydrogen producing simply, does not produce pollutions, product purity height due to its equipment
Receive much concern [W.T.Hong, M.Risch, K.A.Stoerzinger, A.Grimaud, J.Suntivich and etc. feature
Y.Shao-Horn,Toward the rational design of non-precious transition metal
oxides for oxygen electrocatalysis[J],Energy Environ.Sci.,2015,8,1404-1427]。
Owing to the polarization on electrode result in the existence of overpotential of hydrogen evolution, the overpotential height separating out hydrogen when reality is electrolysed means
More electric work is consumed during electrolysis.So, research and development hydrogen-precipitating electrode is it is necessary to have relatively low impedance and relatively low overpotential
[K.Zeng and D.K.Zhang,Recent progress in alkaline water electrolysis for
hydrogen production and applications[J],Prog Energ Combust.,2010,36,307-326]。
Liberation of hydrogen effect quality can use overpotential of hydrogen evolution, Tafel slope and AC impedance to weigh.Overpotential of hydrogen evolution refers to that electrode occurs
Redox onset potential；Tafel curve represents electron number and the reaction mechanism participating in reaction.Overpotential of hydrogen evolution is absolute
Be worth the least, Tafel slope is the least, impedance is the least, means that the resistance of material is the least, electric conductivity is the best, liberation of hydrogen effect is the best.
Business-like platinum electrode has minimum overpotential of hydrogen evolution (close to 0 volt, relative to reversible hydrogen electrode), Ta Feier
Slope is 30mv/dec.Excellent catalytic effect, stable performance, but its expensive, scarcity of resources, look for new replacement type liberation of hydrogen
Electrode is extremely urgent.MoS2It it is one of widely studied hydrogen-precipitating electrode substituting platinum.Present stage, multiple MoS2Synthesis and its
As hydrogen evolution electrode material by reported in literature, but they have certain limitation.Chinese patent (CN 102849798
A) a kind of MoS is provided2The preparation of micron film thin film and for hydrogen evolution electrode material, the MoS that the method prepares2Micron film is erect
It is grown in an orderly manner in substrate, forms MoS2Thin film, this thin film Tafel slope little (52mV/dec), there is higher electrochemistry steady
Qualitative, its shortcoming is to prepare relatively complicated and have higher overpotential of hydrogen evolution (-30mv).Chinese patent (CN 105126876
A) realize the hydro-thermal carbon of biomass by hydro-thermal method and be coated on flower-shaped ZnO surface, with after after high temperature cabonization and acid etch, obtain
Flower-shaped material with carbon element.MoS is finally given for substrate and four thio ammonium molybdate solvent thermal reaction the most again with the flower-shaped carbon of conduction2
Nano-particle is supported on the nano composite material on flower-shaped carbon, the MoS that the method obtains2Complex carbon material has relatively low liberation of hydrogen to be risen
Beginning current potential (～110mV), less Tafel slope (65mV/dec) and stability, its shortcoming is that preparation process is the most loaded down with trivial details.
Document report solvent-thermal method graphene oxide and (NH4)2MoS4In organic solvent reacting by heating prepare micron molybdenum bisuphide with
Graphene composite material [Yanguang Li, Hailiang Wang, Liming Xie, Yongye Liang, Guosong
Hong,and Hongjie Dai,MoS2 Nanoparticles Grown on Graphene:An Advanced
Catalyst for the Hydrogen Evolution Reaction[J],J.Am.Chem.Soc.2011,133,7296-
7299], and as hydrogen-precipitating electrode, overpotential of hydrogen evolution is at about 0.1V, and Tafel slope is 41mv/dec.The method has
The advantages such as overpotential is low, electric current is bigger, but preparation process is loaded down with trivial details, is not easy to industrialized popularization.
Up to now, the MoS reported2Materials synthesis is many to be constructed by the reaction of the method such as hydro-thermal method, solvent-thermal method, for
To the MoS with relatively low overpotential of hydrogen evolution2Material, Graphene or the CNTs etc. of adding have the auxiliary material of high conductance more
Material.The method would generally form the aggregation of larger particles, and is difficult to obtain micron or nanometer materials, and Graphene or carbon
The preparation process of these conducting bases such as nanotube is the most relatively costly, and environmental pollution is bigger, it is difficult to efficiently controlledly synthesis
There is the micron order MoS of relatively low overpotential of hydrogen evolution2Material.
Summary of the invention
It is an object of the invention to provide a kind of micron (1.0～2.0 microns) molybdenum bisuphide (MoS2) Electrocatalytic Activity for Hydrogen Evolution Reaction material
And preparation method thereof.
The present invention selects four cheap hydration ammonium heptamolybdates to be molybdenum source, and thiourea is sulfur source, specific organic molten by selecting
Agent, simple single step reaction prepares micron order MoS2Material.Realize MoS from microcosmic point2Controlledly synthesis, and pass through
Change solvent changes product pattern, and (from lamellar to lamellar heaped-up, embodiment 1 is lamellar, and embodiment 2～4 is lamellar heap
Long-pending), and synthetic product size (1.0～2.0 microns) can be controlled, the method may certify that the selection of solvent is to micron order
MoS2There is large effect in growth and the formation of material, to micron order MoS2The industrialized production of material and the expansion of application thereof
Significant.
A kind of micron order MoS of the present invention2The preparation method of material, its step is as follows:
By four hydration ammonium heptamolybdate (H24Mo7N6O24·4H2O) dissolve in a solvent, be made into 0.025～0.05mol/L
Solution, adds thiourea (CH4N2S), four hydration ammonium heptamolybdates are 1: 30～1: 40 with the mol ratio of thiourea, and stirring makes solution mix
Uniformly, then carry out hydro-thermal reaction, after having reacted, be naturally cooling to room temperature, by centrifugation, washing, obtain micron order after drying
MoS2Material, particle diameter is 1.0～2.0 microns.
Further, described solvent is N, and N '-dimethyl Methanamide, deionized water or volume ratio are the N of 1:1, N '-two
Methylformamide and the mixing of deionized water；
Further, described stirring is magnetic agitation, and mixing speed is 500～1000r/min, mixing time be 30～
40min；
Further, described hydrothermal temperature is 200～220 DEG C, and the hydro-thermal reaction time is 20～24h；
Further, described washing is successively by deionized water and washing with alcohol.
Micron order MoS prepared by the present invention2Material application in electrocatalytic hydrogen evolution reacts: optimal liberation of hydrogen initiates at electricity
Position-0.18v vs.RHE (relative to reversible hydrogen electrode), Tafel slope is 59.5mV/dec, and AC impedance is at 270 ohm.
The present invention is that direct growth goes out orderly stratiform MoS under the conditions of solvent thermal2Micron film, this simple synthetic method,
With low cost, reproducible；The product structure obtained is homogeneous, ordered arrangement；The MoS generated2Material, has and well leads
Electrical property；Additionally, by the concentration and the type of solvent that control initiation material in solution, can synthesize that to have different size big
Little micron film.This micron film has good Hydrogen Evolution Performance, and (take-off potential is (electric relative to reversible hydrogen for-0.18v vs.RHE
Pole)), there is the application prospect that good industrialized production is basic and wide.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the platelike molybdenumdisulfide micron film obtained by the embodiment of the present invention 1～4.This figure illustrates in reality
Execute that obtain in example 1～4 is all highly purified molybdenum bisuphide；
Fig. 2 is molybdenum bisuphide micron film electron scanning micrograph (SEM) that the embodiment of the present invention 1 prepares；
From Figure 2 it can be seen that MoS2Micron film a size of 1.7 microns
Fig. 3 is molybdenum bisuphide micron film electron scanning micrograph (SEM) that the embodiment of the present invention 2 prepares；
MoS as seen from Figure 32Micron film a size of 1.47 microns, and MoS2There is agglomeration, reunion suppression catalysis is lived
The performance of property.
Fig. 4 is molybdenum bisuphide micron film field scanning electron micrograph (SEM) that the embodiment of the present invention 3 prepares；
MoS as seen from Figure 42Micron film a size of 1.95 microns, and MoS2There is agglomeration, reunion suppression catalysis is lived
The performance of property.
Fig. 5 is molybdenum bisuphide micron film electron scanning micrograph (SEM) that the embodiment of the present invention 4 prepares；
MoS as seen from Figure 52Micron film a size of 1.0 microns, and MoS2There is agglomeration, reunion suppression catalysis activity
Performance.
Fig. 6 is molybdenum bisuphide sample linear sweep voltammetry (LSV) curve that the embodiment of the present invention 1～4 prepares；
It will be appreciated from fig. 6 that the take-off potential of the curve 1 of embodiment 1 correspondence is that (vs.RHE is relative to reversible hydrogen electricity for-0.18v
Pole), the take-off potential of the curve 2 of embodiment 2 correspondence is-0.20V (vs.RHE is relative to reversible hydrogen electrode), and embodiment 3 is corresponding
The take-off potential of curve 3 be-0.21V (vs.RHE is relative to reversible hydrogen electrode), the initial electricity of the curve 4 of embodiment 4 correspondence
Position is-0.21V (vs.RHE is relative to reversible hydrogen electrode).The take-off potential of this figure explanation embodiment 1 is 1～4 embodiment
Middle take-off potential is minimum, and along with the increase of overpotential, cathode-current density increases rapidly, illustrates that embodiment 1 has higher
Exchange current density and cathode-current density.
Fig. 7 is Tafel curve (Tafel) figure of the molybdenum bisuphide sample that the embodiment of the present invention 1～4 prepares；Can by Fig. 7
Knowing, the Tafel slope of the curve 1 of embodiment 1 correspondence is 59.5mV/dec, the Tafel slope of the curve 2 of embodiment 2 correspondence
Being 57.3mV/dec, the Tafel slope of the curve 3 of embodiment 3 correspondence is 125.9mV/dec, the curve 4 of embodiment 4 correspondence
Tafel slope is 55.2mV/dec.Less Tafel slope is more beneficial for actual application, because having oblique compared with trourelle Fei Er
The eelctro-catalyst of rate will reach faster oxygen evolution reaction speed along with the rising of additional overpotential.This figure explanation embodiment 1
Tafel curve slope is relatively low it was confirmed the embodiment 1 enhancement effect to evolving hydrogen reaction catalysis activity, advantageously anti-in liberation of hydrogen
Should.
Fig. 8 is the molybdenum bisuphide micron film electrochemistry hydrogen manufacturing impedance spectrum that the embodiment of the present invention 1～4 prepares；
As shown in Figure 8, the impedance of the curve 1 of embodiment 1 correspondence is 270 ohm to the maximum, the curve 2 of embodiment 2 correspondence
Impedance is 360 ohm to the maximum, and the impedance of the curve 3 of embodiment 3 correspondence is 540 ohm to the maximum, and impedance is slightly higher, and embodiment 4 is corresponding
The impedance of curve 4 more than 800 ohm, be that these four sample impedances are maximum.This figure explanation embodiment 1 has the electric charge of minimum
Transfer resistance, conductive capability is the strongest, beneficially evolving hydrogen reaction.
Detailed description of the invention
Embodiment 1
0.31g (0.00025mol) four hydration ammonium heptamolybdate is dissolved into 10.0mL N, in N '-dimethyl Methanamide, joins
Make the solution of 0.025mol/L, add 0.57g (0.0075mol) thiourea, utilize magnetic stirring apparatus (500r/min) to stir
30min, transfers to, in the hydrothermal reaction kettle that volume is 30mL, carry out hydro-thermal reaction under the conditions of 220 DEG C by the solution after stirring
24h, then natural cooling, by centrifugation, successively with being dried to obtain 0.42g molybdenum bisuphide micron after deionized water and washing with alcohol again
Sheet Electrocatalytic Activity for Hydrogen Evolution Reaction agent.It can be observed from fig. 2 that product is micron film Rotating fields.
Use three-electrode system enterprising at electrochemical workstation (Gamry Reference 600 Instruments, USA)
Row test.The molybdenum bisuphide prepared by 5.0mg the present embodiment disperses as catalyst and 20.0 μ L Nafion (5wt%) solution
In alcohol-water mixed solution (ethanol: the volume ratio of water is 1:1), supersound process obtains uniform dispersion liquid in 1 hour.Then
10.0 these dispersion liquids of μ L are supported on the glass-carbon electrode of a diameter of 3 millimeters.Use the H of 0.5M2SO4As electrolyte (with purity nitrogen
Gas bell removes dissolved oxygen in 30 minutes), Ag/AgCl electrode, is loaded with urging as to electrode as reference electrode, high purity graphite rod
The glass-carbon electrode of agent is as working electrode, with 20mV s-1Sweep speed and carry out the measurement of polarization curve.Record the initial of embodiment 1
Hydrogen-evolution overpotential is-0.18v (vs.RHE is relative to reversible hydrogen electrode), and Tafel slope is 59.5mV/dec, and impedance is 270 to the maximum
Ohm.From data above, the molybdenum bisuphide micron film that this example obtains has good catalytic activity for hydrogen evolution.
Embodiment 2
0.31g (0.00025mol) four hydration ammonium heptamolybdate is dissolved into 10mL N, N '-dimethyl Methanamide/deionization
In water (volume ratio=1:1) mixed solution, it is configured to the solution of 0.025mol/L, adds 0.57g (0.0075mol) thiourea,
Utilize magnetic stirrer 30min (mixing speed 1000r/min), the solution after stirring is transferred to the water that volume is 30mL
In thermal response still, carrying out hydro-thermal reaction 24h, then natural cooling under the conditions of 220 DEG C, by centrifugation, deionized water and ethanol washes
Being dried to obtain 0.37g molybdenum bisuphide micron film after washing again, as seen from Figure 3, product is micron film Rotating fields, but starts to send out
Raw reunion.
Use three-electrode system enterprising at electrochemical workstation (Gamry Reference 600 Instruments, USA)
Row test.The molybdenum bisuphide prepared by 5.0mg the present embodiment disperses as catalyst and 20.0 μ L Nafion (5wt%) solution
In alcohol-water mixed solution (ethanol: the volume ratio of water is 1:1), supersound process obtains uniform dispersion liquid in 1 hour.Then
10.0 μ L dispersion liquids are supported on the glass-carbon electrode of a diameter of 3 millimeters.Use the H of 0.5M2SO4As electrolyte (with pure nitrogen gas
Bubbling removes dissolved oxygen in 30 minutes), Ag/AgCl electrode as to electrode, is loaded with catalysis as reference electrode, high purity graphite rod
The glass-carbon electrode of agent is as working electrode, with 20mV s-1Sweep speed and carry out the measurement of polarization curve.Record the initial analysis of embodiment 2
Hydrogen potential is-0.20V (vs.RHE is relative to reversible hydrogen electrode), and Tafel slope is 57.3mV/dec, and impedance is 360 Europe to the maximum
Nurse.From data above, the molybdenum bisuphide material that this example obtains has good catalytic activity for hydrogen evolution.
Embodiment 3
0.62g (0.0005mol) four hydration ammonium heptamolybdate is dissolved into 10mL N, N '-dimethyl Methanamide/deionized water
In (volume ratio=1:1) mixed solution, it is configured to the solution of 0.05mol/L, adds 1.14g (0.015mol) thiourea, utilize
Magnetic stirrer 30min (mixing speed 1000r/min), transfers to, by the solution after stirring, the hydro-thermal that volume is 30mL anti-
Answer in still, under the conditions of 220 DEG C, carry out hydro-thermal reaction 24h, then natural cooling, by centrifugation, after deionized water and washing with alcohol
It is dried to obtain 0.68g molybdenum bisuphide micron film again, from fig. 4 it can be seen that product agglomeration is serious.
Use three-electrode system enterprising at electrochemical workstation (Gamry Reference 600 Instruments, USA)
Row test.The molybdenum bisuphide prepared by 5.0mg the present embodiment disperses as catalyst and 20.0 μ L Nafion (5wt%) solution
In alcohol-water mixed solution (ethanol: the volume ratio of water is 1:1), supersound process obtains uniform dispersion liquid in 1 hour.Then
10.0 μ L dispersion liquids are supported on the glass-carbon electrode of a diameter of 3 millimeters.Use the H of 0.5M2SO4As electrolyte (with pure nitrogen gas
Bubbling removes dissolved oxygen in 30 minutes), Ag/AgCl electrode as to electrode, is loaded with catalysis as reference electrode, high purity graphite rod
The glass-carbon electrode of agent is as working electrode, with 20mV s-1Sweep speed and carry out the measurement of polarization curve.Record the initial analysis of embodiment 3
Hydrogen potential is-0.21V (vs.RHE is relative to reversible hydrogen electrode), and Tafel slope is 125.9mV/dec, and impedance is 540 to the maximum
Ohm.From data above, the molybdenum bisuphide material that this example obtains has relatively common catalytic activity for hydrogen evolution.
Embodiment 4
0.62g (0.0005mol) four hydration ammonium heptamolybdate is dissolved in 10mL deionized water solution, is configured to
The solution of 0.05mol/L, adds 1.14g (0.015mol) thiourea, utilizes magnetic stirrer 30min (mixing speed
1000r/min), transfer to, in the hydrothermal reaction kettle that volume is 30mL, under the conditions of 200 DEG C, carry out hydro-thermal by the solution after stirring
Reaction 20h, then natural cooling, by centrifugation, be dried to obtain 0.65g molybdenum bisuphide micron after deionized water and washing with alcohol again
Sheet, as seen from Figure 3, product is micron film Rotating fields, but starts to reunite.
Use three-electrode system enterprising at electrochemical workstation (Gamry Reference 600 Instruments, USA)
Row test.The molybdenum bisuphide prepared by 5.0mg the present embodiment disperses as catalyst and 20.0 μ L Nafion (5wt%) solution
In alcohol-water mixed solution (ethanol: the volume ratio of water is 1:1), supersound process obtains uniform dispersion liquid in 1 hour.Then
10.0 μ L dispersion liquids are supported on the glass-carbon electrode of a diameter of 3 millimeters.Use the H of 0.5M2SO4As electrolyte (with pure nitrogen gas
Bubbling removes dissolved oxygen in 30 minutes), Ag/AgCl electrode as to electrode, is loaded with catalysis as reference electrode, high purity graphite rod
The glass-carbon electrode of agent is as working electrode, with 20mV s-1Sweep speed and carry out the measurement of polarization curve.Record the initial analysis of embodiment 4
Hydrogen potential is-0.21V (vs.RHE is relative to reversible hydrogen electrode), and Tafel slope is 55.2mV/dec, and impedance is more than 800 Europe
Nurse.From data above, the molybdenum bisuphide material that this example obtains has poor catalytic activity for hydrogen evolution.
Claims (7)
1. the preparation method of a micron molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material, it is characterised in that: by four hydration ammonium heptamolybdates
H24Mo7N6O24·4H2O dissolves in a solvent, is made into the solution of 0.025～0.05mol/L, adds thiourea CH4N2S, four hydrations seven
Ammonium molybdate is 1: 30～1: 40 with the mol ratio of thiourea, and stirring makes solution mix homogeneously, then carries out hydro-thermal reaction, and reaction completes
After be naturally cooling to room temperature, by centrifugation, washing, obtain micron order molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material after drying.
The preparation method of a kind of micron of molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material the most as claimed in claim 1, it is characterised in that: institute
The solvent stated is N, and N '-dimethyl Methanamide, deionized water or volume ratio are the N of 1:1, N '-dimethyl Methanamide and deionization
The mixing of water.
The preparation method of a kind of micron of molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material the most as claimed in claim 1, it is characterised in that: institute
The stirring stated is magnetic agitation, and mixing speed is 500～1000r/min, and mixing time is 30～40min.
The preparation method of a kind of micron of molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material the most as claimed in claim 1, it is characterised in that: institute
The hydrothermal temperature stated is 200～220 DEG C, and the hydro-thermal reaction time is 20～24h.
The preparation method of a kind of micron of molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material the most as claimed in claim 1, it is characterised in that: institute
The washing stated is for successively by deionized water and washing with alcohol.
6. a micron molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material, it is characterised in that: it is by described in Claims 1 to 5 any one
Method prepare.
7. the application in terms of evolving hydrogen reaction of the micron molybdenum bisuphide Electrocatalytic Activity for Hydrogen Evolution Reaction material described in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610459534.XA CN106040264A (en) | 2016-06-23 | 2016-06-23 | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610459534.XA CN106040264A (en) | 2016-06-23 | 2016-06-23 | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106040264A true CN106040264A (en) | 2016-10-26 |
Family
ID=57168867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610459534.XA Pending CN106040264A (en) | 2016-06-23 | 2016-06-23 | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106040264A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521549A (en) * | 2016-11-16 | 2017-03-22 | 武汉理工大学 | Production method of field effect electrocatalytic hydrogen production device based on MoS2 nanosheet |
| CN107098390A (en) * | 2017-04-20 | 2017-08-29 | 合肥学院 | One kind simply prepares the adjustable sheet self assembly MoS of particle diameter2The method of bobbles shape powder |
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108191075A (en) * | 2017-12-29 | 2018-06-22 | 太原学院 | MoS in a kind of microorganism electrolysis cell2The preparation method and application of the compound hydrogen-precipitating electrode of/transition metal/graphene |
| CN108404938A (en) * | 2018-04-05 | 2018-08-17 | 哈尔滨工业大学 | A kind of electrocatalytic hydrogen evolution MoS2Nano flower sphere catalyst and preparation method thereof |
| CN109037641A (en) * | 2018-08-07 | 2018-12-18 | 河源广工大协同创新研究院 | A kind of lithium ion battery MoS2The preparation method of negative electrode material |
| CN109622044A (en) * | 2018-12-19 | 2019-04-16 | 郑州大学 | A kind of efficient liberation of hydrogen catalyst material, preparation method and application |
| CN110327946A (en) * | 2019-08-09 | 2019-10-15 | 黑龙江科技大学 | A kind of molybdenum disulfide/nickelous selenide composite material and preparation method and application |
| CN110339846A (en) * | 2019-07-03 | 2019-10-18 | 西南大学 | MoS2The preparation and application of/ZnO liberation of hydrogen catalyst |
| CN113249753A (en) * | 2021-04-07 | 2021-08-13 | 上海应用技术大学 | Molybdenum sulfide @ cobalt-MOF/NF hydrogen evolution material and in-situ synthesis method and application |
| CN113668008A (en) * | 2021-08-25 | 2021-11-19 | 常州大学 | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof |
| CN114045522A (en) * | 2021-11-29 | 2022-02-15 | 中国石油大学(华东) | NiMo6-S @ HCS nano composite material, preparation method and application in electrocatalytic hydrogen production |
| CN114674904A (en) * | 2022-02-23 | 2022-06-28 | 江苏大学 | MoS based on magnetic control2Construction method of label-free electrochemical aptamer sensing platform of nanosheet |
| CN114768530A (en) * | 2022-04-29 | 2022-07-22 | 中国工程物理研究院材料研究所 | Application of molybdenum disulfide in hydrogen isotope electrolytic separation |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861284A (en) * | 2007-09-14 | 2010-10-13 | 丰田自动车株式会社 | Single-crystal fine powder of sulfide or sulfide complex and method for preparing the same |
| WO2012040111A1 (en) * | 2010-09-23 | 2012-03-29 | Conocophillips Company | Sulfur-tolerant catalyst prepared through high pressure decomposition |
| CN102849798A (en) * | 2012-08-29 | 2013-01-02 | 北京化工大学 | Molybdenum disulfide nano-sheet film material and its preparation methods |
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104961353A (en) * | 2015-06-24 | 2015-10-07 | 中国科学院上海光学精密机械研究所 | Method for preparing large-size layered orthorhombic MoS2 nano-film of asymmetric structure under hydrothermal condition |
| CN105174311A (en) * | 2015-07-25 | 2015-12-23 | 复旦大学 | Molybdenum disulfide nanosheet/carbon aerogel hybrid material and preparation method therefor |
| CN105624756A (en) * | 2015-12-29 | 2016-06-01 | 中国石油大学(华东) | High-activity molybdenum sulfide film electrocatalyst and preparation method thereof |
-
2016
- 2016-06-23 CN CN201610459534.XA patent/CN106040264A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101861284A (en) * | 2007-09-14 | 2010-10-13 | 丰田自动车株式会社 | Single-crystal fine powder of sulfide or sulfide complex and method for preparing the same |
| WO2012040111A1 (en) * | 2010-09-23 | 2012-03-29 | Conocophillips Company | Sulfur-tolerant catalyst prepared through high pressure decomposition |
| CN102849798A (en) * | 2012-08-29 | 2013-01-02 | 北京化工大学 | Molybdenum disulfide nano-sheet film material and its preparation methods |
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104961353A (en) * | 2015-06-24 | 2015-10-07 | 中国科学院上海光学精密机械研究所 | Method for preparing large-size layered orthorhombic MoS2 nano-film of asymmetric structure under hydrothermal condition |
| CN105174311A (en) * | 2015-07-25 | 2015-12-23 | 复旦大学 | Molybdenum disulfide nanosheet/carbon aerogel hybrid material and preparation method therefor |
| CN105624756A (en) * | 2015-12-29 | 2016-06-01 | 中国石油大学(华东) | High-activity molybdenum sulfide film electrocatalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴壮志等: "《钨钼硫化物的制备与性能》", 30 October 2015, 中南大学出版社 * |
| 王丽姣: "二硫化钼及其复合物的制备和光解水产氢性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521549A (en) * | 2016-11-16 | 2017-03-22 | 武汉理工大学 | Production method of field effect electrocatalytic hydrogen production device based on MoS2 nanosheet |
| CN107098390A (en) * | 2017-04-20 | 2017-08-29 | 合肥学院 | One kind simply prepares the adjustable sheet self assembly MoS of particle diameter2The method of bobbles shape powder |
| CN107098390B (en) * | 2017-04-20 | 2018-10-16 | 合肥学院 | One kind simply preparing the adjustable sheet self assembly MoS of grain size2The method of bobbles shape powder |
| CN108191075B (en) * | 2017-12-29 | 2021-01-08 | 太原学院 | MoS in microbial electrolysis cell2Preparation method and application of/transition metal/graphene composite hydrogen evolution electrode |
| CN108191075A (en) * | 2017-12-29 | 2018-06-22 | 太原学院 | MoS in a kind of microorganism electrolysis cell2The preparation method and application of the compound hydrogen-precipitating electrode of/transition metal/graphene |
| CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
| CN108404938A (en) * | 2018-04-05 | 2018-08-17 | 哈尔滨工业大学 | A kind of electrocatalytic hydrogen evolution MoS2Nano flower sphere catalyst and preparation method thereof |
| CN109037641A (en) * | 2018-08-07 | 2018-12-18 | 河源广工大协同创新研究院 | A kind of lithium ion battery MoS2The preparation method of negative electrode material |
| CN109622044A (en) * | 2018-12-19 | 2019-04-16 | 郑州大学 | A kind of efficient liberation of hydrogen catalyst material, preparation method and application |
| CN110339846A (en) * | 2019-07-03 | 2019-10-18 | 西南大学 | MoS2The preparation and application of/ZnO liberation of hydrogen catalyst |
| CN110327946A (en) * | 2019-08-09 | 2019-10-15 | 黑龙江科技大学 | A kind of molybdenum disulfide/nickelous selenide composite material and preparation method and application |
| CN110327946B (en) * | 2019-08-09 | 2022-02-08 | 哈尔滨师范大学 | Molybdenum disulfide/nickel selenide composite material and preparation method and application thereof |
| CN113249753A (en) * | 2021-04-07 | 2021-08-13 | 上海应用技术大学 | Molybdenum sulfide @ cobalt-MOF/NF hydrogen evolution material and in-situ synthesis method and application |
| CN113249753B (en) * | 2021-04-07 | 2022-07-19 | 上海应用技术大学 | Molybdenum sulfide @ cobalt-MOF/NF hydrogen evolution material and in-situ synthesis method and application |
| CN113668008A (en) * | 2021-08-25 | 2021-11-19 | 常州大学 | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof |
| CN114045522A (en) * | 2021-11-29 | 2022-02-15 | 中国石油大学(华东) | NiMo6-S @ HCS nano composite material, preparation method and application in electrocatalytic hydrogen production |
| CN114674904A (en) * | 2022-02-23 | 2022-06-28 | 江苏大学 | MoS based on magnetic control2Construction method of label-free electrochemical aptamer sensing platform of nanosheet |
| CN114768530A (en) * | 2022-04-29 | 2022-07-22 | 中国工程物理研究院材料研究所 | Application of molybdenum disulfide in hydrogen isotope electrolytic separation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106040264A (en) | Micron molybdenum disulfide hydrogen evolution electro-catalytic material, preparation method and application of micron molybdenum disulfide hydrogen evolution electro-catalytic material | |
| Xu et al. | Ultra-uniform PdBi nanodots with high activity towards formic acid oxidation | |
| Zhu et al. | Ru-modified silicon nanowires as electrocatalysts for hydrogen evolution reaction | |
| Wang et al. | Formation of hierarchical Co-decorated Mo2C hollow spheres for enhanced hydrogen evolution | |
| Wang et al. | Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media | |
| CN107267124A (en) | A kind of nitrogenous graphitized carbon material containing the bimetallic MOFs of Ni/Fe | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| CN103816894B (en) | Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof | |
| Qiao et al. | Micrometer‒Scale biomass carbon tube matrix auxiliary MoS2 heterojunction for electrocatalytic hydrogen evolution | |
| Yan et al. | Porous β-Mo2C nanoparticle clusters supported on walnut shell powders derived carbon matrix for hydrogen evolution reaction | |
| CN107746051A (en) | A kind of nitrogen-doped graphene nanobelt nano-cobaltic-cobaltous oxide hybrid material and preparation method thereof | |
| Huang et al. | Well-dispersive Pt nanoparticles grown on 3D nitrogen-and sulfur-codoped graphene nanoribbon architectures: highly active electrocatalysts for methanol oxidation | |
| CN105797758A (en) | Synthetic method for graphene-loaded MoO2-Mo2C | |
| Chen et al. | Castoff derived Biomass‒carbon supported MoS2 nanosheets for hydrogen evolution reaction | |
| CN108461763A (en) | A kind of cobalt disulfide/sulfur and nitrogen co-doped graphene catalysis material and preparation and application | |
| CN108232213A (en) | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof | |
| Akinay et al. | Synthesis of 3D Sn doped Sb2O3 catalysts with different morphologies and their effects on the electrocatalytic hydrogen evolution reaction in acidic medium | |
| Zhang et al. | 3D Pt/MoO3 nanocatalysts fabricated for effective electrocatalytic oxidation of alcohol | |
| CN107685150A (en) | A kind of Ni ＆ MoO of nitrogen-doped carbon cladding2Superfine nanowire and its preparation method and application | |
| Cheng et al. | CoS nanowires mediated by superionic conductor Ag2S for boosted oxygen evolution | |
| Li et al. | Bimetallic Ni-Hf tellurides as an advanced electrocatalyst for overall water splitting with layered g-C3N4 modification | |
| Jiang et al. | Highly efficient hydrogen evolution reaction of Co 3 O 4 supports on N-doped carbon nanotubes in an alkaline solution | |
| CN107321372A (en) | The preparation method of CoS nano particles/N doping RGO liberation of hydrogen composites | |
| CN108097269A (en) | A kind of ultra-thin porous Ce-Ni-O-S nanometer sheets and its preparation method and application | |
| CN107335433A (en) | A kind of preparation method for aoxidizing molybdenum base efficient electric catalytic hydrogen evolution catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161026 |