CN106964371A - A kind of porous carbon load molybdenum disulfide nano sheet composite and preparation method and application - Google Patents
A kind of porous carbon load molybdenum disulfide nano sheet composite and preparation method and application Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 239000002135 nanosheet Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 238000013021 overheating Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 230000010287 polarization Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a kind of porous carbon load molybdenum disulfide nano sheet composite and preparation method and application.The preparation method, comprises the following steps：(1) porous carbon adsorption molybdate is utilized, predecessor is obtained；(2) under an inert atmosphere, the predecessor is heat-treated；Sulfur vapor carries out vulcanization reaction with the predecessor through Overheating Treatment, you can obtain the porous carbon load molybdenum disulfide nano sheet composite.The present invention is come confinement molybdenum disulfide presoma using porous carbon adsorption; the ultra-thin molybdenum sulfide nanometer sheet of small size that feed precursor is converted into by high degree of dispersion by vulcanisation operation again; relative to other methods such as lithium ion graft process, vapour deposition process, hydro-thermal method and solvent-thermal method; this method cost is relatively low, technique is simple, product is clear and definite, suitable for large-scale production；Gained composite water electrolysis hydrogen production catalytic performance is excellent, is better than the other same type catalyst reported.
Description
Technical field
Prepared the invention belongs to nano material and catalysis technical field, more particularly to a kind of porous carbon load molybdenum disulfide is received
Rice piece composite and preparation method and application.
Background technology
The fast development of graphene research in recent years so that two-dimensional layer material turns into study hotspot, this stratiform again
Structure is to stack to form by Interaction between layers power, and with the reduction of dimension, material in electronics structure with block
Material is compared to having significantly different, and this just makes it show good application prospect in microelectronic and catalytic field.
Molybdenum disulfide is a kind of layered semiconductor material similar to graphene film Rotating fields, not only with excellent electricity
Performance, but also with good catalytic activity, receive increasing people's concern.Individual layer molybdenum disulfide is by S-Mo-S tri-
The former molecular interlayer structure of layer, thickness is 0.65 nanometer, and direct band gap is 1.78 electron volts, and these features cause individual layer and block
Body material is compared and had a clear superiority.In addition, the edge of molybdenum disulfide is good catalytic active center.Recent study table
Bright, molybdenum disulfide has electro catalytic activity for Hydrogen evolving reaction (HER), can be used for the preparation of Hydrogen Energy, and this causes it in electrolysis water
Hydrogen preparation field has good application potential.Although molybdenum disulfide can show certain catalytic performance, micron order and block
Body phase molybdenum disulfide catalytic activity is extremely low, and application value is smaller, only when the size reduction of molybdenum disulfide is to nanoscale, and is one
When layer or several Rotating fields, its significant catalytic performance can just be displayed.
Preparing the method for molybdenum disulfide nano thin slice at present has：1) lithium ion graft process, but must be under anhydrous and oxygen-free
Carry out, experimental period is long, and the molybdenum disulfide nano thin slice defect prepared is more；2) mechanical stripping method, yield is few, it is impossible to extensive
Using；3) chemical deposition, yield is considerably less, and accessory substance is more；4) hydrothermal synthesis method, preparation process is complicated, and yield is few, it is impossible to advise
Modelling is used.Generally speaking, above method all suffers from various problems, especially in actual water electrolysis hydrogen production catalytic applications not
Beneficial to the exposure of avtive spot, and easily cause the loss in effective site.
The content of the invention
It is an object of the invention to provide a kind of porous carbon load molybdenum disulfide nano sheet composite and preparation method thereof with
Using, in the composite, molybdenum disulfide nano sheet is highly dispersed on porous carbon support, monodispersity is good, be evenly distributed and
It is controllable, and during as water electrolysis hydrogen production catalyst, show excellent producing hydrogen, catalyzing activity.
A kind of porous carbon that the present invention is provided loads the preparation method of molybdenum disulfide nano sheet composite, including following step
Suddenly：
(1) porous carbon adsorption molybdate is utilized, predecessor is obtained；
(2) under an inert atmosphere, the predecessor is heat-treated；Sulfur vapor is carried out with the predecessor through Overheating Treatment
Vulcanization reaction, you can obtain the porous carbon load molybdenum disulfide nano sheet composite.
In above-mentioned preparation method, step (1), the mass ratio of the porous carbon and the molybdate can be 12：(1~
40), concretely 12：(5~40), 12：(5~30), 12：(5~20), 12：(5~10), 12：5、12：10、12：20、12：
40, preferably 12：5.
In above-mentioned preparation method, step (1), the porous carbon can for it is any be commercially available from commercial channels or according to
The carbon material with loose structure that conventional method is prepared, in a particular embodiment of the present invention, the porous carbon can be
Ketjen black.The aperture of the porous carbon and specific surface area are unrestricted, in a particular embodiment of the present invention, the porous carbon
Aperture can be 0.5~20 nanometer, and specific surface area can be 1400m2/g。
In above-mentioned preparation method, step (1), the molybdate can be the solubilities such as ammonium molybdate, sodium molybdate and potassium molybdate
One or more in molybdate.
Above-mentioned preparation method, the concrete operations of step (1) are as follows：The porous carbon and the molybdate are dispersed in water
In, centrifuged after standing adsorption, collect solid and be dried in vacuo, obtain predecessor.
The porous carbon quality and the volume ratio of water can be (30~120) gram：5 liters, concretely 60 grams：5 liters.
The time of the standing adsorption can be 12~36 hours, concretely 24 hours.
The vacuum drying temperature can be 50~100 DEG C, concretely 60 DEG C；Vacuum drying time can be small for 12~36
When, concretely 24 hours；Vacuum can be -0.05~-0.2 MPa, concretely -0.1 MPa.
In above-mentioned preparation method, step (2), the temperature of the heat treatment can be 500~700 DEG C, preferably 600 DEG C；When
Between can be 0.5~3 hour, preferably 2 hours.
In above-mentioned preparation method, step (2), the mass ratio of the sulfur vapor and the predecessor can be 1：(10~
50), preferably 1：20.
In above-mentioned preparation method, step (2), the temperature of the vulcanization reaction can be 500~700 DEG C, concretely 500
DEG C, 600 DEG C or 700 DEG C, preferably 600 DEG C；Time can be 0.25~3 hour, concretely 1~3 hour, 1 hour or 3 hours,
It is preferred that 1 hour.
Above-mentioned preparation method, the step (2) can be carried out in dual temperature area heating furnace, and concrete operations are as follows：
2-1) the direction being passed through along the inert gas, the predecessor is placed under dual temperature area heating furnace
Trip, sulphur powder is placed in the upstream of dual temperature area heating furnace；
2-2) under the downstream temperature (heat treatment temperature), the predecessor is heat-treated；In the upstream temperature
Spend under (sulphur powder sublimation temperature), sulphur powder is distilled, the sulfur vapor is obtained；While the distillation is carried out, institute is kept
Downstream temperature is stated, it is anti-that the sulfur vapor carries out the vulcanization under the downstream temperature with the predecessor Jing Guo the heat treatment
Should, you can obtain the porous carbon load molybdenum disulfide nano sheet composite.
Above-mentioned preparation method, the sublimation temperature of the sulphur powder can be 300~500 DEG C, concretely 300 DEG C.
Invention further provides the porous carbon load that a kind of preparation method as described in any of the above-described is prepared
Molybdenum disulfide nano sheet composite.In the composite, the number of plies of molybdenum disulfide nano sheet can be 1~3 layer, size range
It can be 2~10 nanometers；Molybdenum disulfide nano sheet dimensional height is dispersed on porous carbon support, monodispersity is good, be evenly distributed and
It is controllable.In the composite, the weight/mass percentage composition of molybdenum disulfide nano sheet can be 10~50%, preferably 15~25%, carry
Amount is controllable.
Present invention also offers above-mentioned porous carbon load molybdenum disulfide nano sheet composite answering in water electrolysis hydrogen production
With.
Electro-chemical test shows that porous carbon load molybdenum disulfide nano sheet composite provided by the present invention is used as electrolysis
Water catalyst for preparing hydrogen, its producing hydrogen, catalyzing performance is better than same type material.Preparation method of the present invention is simple, operating process is easy, raw
Production cost is low, be easy to mass production, with wide industrial applications prospect.
The present invention compared with prior art, has the characteristics that：
1st, the present invention is come confinement molybdenum disulfide presoma, then by vulcanisation operation by feed precursor using porous carbon adsorption
The ultra-thin molybdenum sulfide nanometer sheet of small size of high degree of dispersion is converted into, relative to other methods such as lithium ion graft process, gas phase
Sedimentation, hydro-thermal method and solvent-thermal method, this method cost is relatively low, technique is simple, product is clear and definite, suitable for large-scale production.
2nd, the porous carbon selected by the present invention is simple and easy to get, with loose structure, there is high specific surface area and many micro- Jie
Hole, can show excellent space confinement effect.
3rd, the porous carbon load molybdenum disulfide nano sheet composite water electrolysis hydrogen production catalytic performance that prepared by the present invention is excellent,
It is better than the other same type catalyst reported.
Brief description of the drawings
Fig. 1 prepares schematic diagram for porous carbon of the present invention load molybdenum disulfide nano sheet composite.
The x-ray powder of porous carbon load molybdenum disulfide nano sheet composites of the Fig. 2 to be prepared in embodiment 1 spreads out
Penetrate curve picture.
The Raman light of porous carbon load molybdenum disulfide nano sheet composites of the Fig. 3 to be prepared in embodiment 1 is set a song to music
Line chart piece.
The transmission electron microscope of porous carbon load molybdenum disulfide nano sheet composites of the Fig. 4 to be prepared in embodiment 1 shines
Piece and grain size distribution, wherein, Fig. 4 (a) is that low power transmission electron microscope photo, Fig. 4 (b) are high-resolution-ration transmission electric-lens photo, Fig. 4
(c) it is grain size distribution.
Fig. 5 is the TGA thermogravimetric analysis of the porous carbon load molybdenum disulfide nano sheet composite prepared in embodiment 1
As a result.
Fig. 6 is that porous carbon load molybdenum disulfide nano sheet composite, the physics of comparative example 1 that embodiment 1 is prepared are mixed
Close the electrolytic hydrogen production reaction polarization curve map of business molybdenum disulfide powder in molybdenum disulfide material prepared by vulcanization, and contrast 2.
Fig. 7 is the transmission electron microscope photo of the molybdenum disulfide nano sheet prepared in comparative example 1.
Embodiment
Molybdenum disulfide nano sheet composite and preparation method thereof is loaded to porous carbon with answering below by way of specific embodiment
With being further described in detail, but the invention is not limited in following embodiments.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite is prepared according to schematic diagram shown in Fig. 1, is comprised the following steps that：
(1) by purchased from the Ketjen black of Japanese LION companies, (model ECP-600JD, aperture is 0.5~20 nanometer, compares surface
Product is 1400m2/ g) porous carbon and ammonium molybdate mass ratio be 12：5 (porous carbon is 60 milligrams, and ammonium molybdate is 25 milligrams) add 5 millis
In liter deionized water, ultrasonic disperse is uniform, and centrifugation is washed after being standing and soak for absorption 24 hours, is under -0.1 MPa 60 in vacuum
DEG C dry 24 hours, obtain predecessor；
(2) predecessor is transferred to the downstream (downstream in the direction being passed through along gas) of dual temperature area heating furnace, and
Excessive sulphur powder is placed in upstream (upstream that direction is passed through along gas), and (mass ratio of sulphur powder and predecessor is 1：20)；Protected in argon gas
Under shield, downstream powder is annealed 2 hours at 600 DEG C；Then make upstream sulphur powder in 300 DEG C of distillations, keep downstream temperature, make upstream
The sulfur vapor that sulphur powder is produced reacts 1 hour with the downstream powder by annealing under downstream temperature (600 DEG C), is cooled to room temperature,
Produce porous carbon load molybdenum disulfide nano sheet composite.
The X-ray powder diffraction curve of porous carbon load molybdenum disulfide nano sheet composite manufactured in the present embodiment is as schemed
Shown in 2, observation understands that molybdenum disulfide nano sheet size manufactured in the present embodiment is smaller so that only there is wider molybdenum disulfide
Diffraction maximum.The Raman diffused light spectral curve of the ultra-thin molybdenum disulfide nano sheet of small size for the high degree of dispersion being supported on porous carbon is such as
Shown in Fig. 3, observation is understood, the curve is the molybdenum disulfide curve of standard, shows that product obtains molybdenum disulfide.
The transmission electron microscope photo of porous carbon manufactured in the present embodiment load molybdenum disulfide nano sheet composite and
Grain size distribution is as shown in figure 4, wherein Fig. 4 (a) is low power transmission electron microscope photo, and Fig. 4 (b) is high-resolution-ration transmission electric-lens
Photo, Fig. 4 (c) is grain size distribution.From Fig. 4 (a), the ultra-thin curing of small size of high degree of dispersion manufactured in the present embodiment
Molybdenum nanometer sheet is to be highly dispersed to be supported on porous carbon, and Fig. 4 (b) and 4 (c) understand that molybdenum disulfide nano sheet average grain diameter is
2.8 nanometers ± 0.5 nanometer, the lattice fringe image in Fig. 4 (b) proves that the nanometer sheet is molybdenum disulfide nano sheet.
The thermogravimetric curve of porous carbon manufactured in the present embodiment load molybdenum disulfide nano sheet composite as shown in figure 5, through
It is 15.05% to calculate obtained molybdenum disulfide negative mass percentage composition.
From above-mentioned data, the method that the present invention is provided is fully able to preparation and is highly dispersed on porous carbon, and carrying capacity can
Control, the number of plies is based on 1 layer and the less ultra-thin molybdenum disulfide nano sheet of size.
The water electrolysis hydrogen production reaction polarization of porous carbon load molybdenum disulfide nano sheet composite manufactured in the present embodiment is bent
Line is as shown in Figure 6.Specific experiment step is：The water electrolysis hydrogen production reaction polarization curve rotating ring disk electrode (r.r.d.e) of material rubs 0.5
You/liter sulfuric acid solution in measure, the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and polarization curve sweep speed is 5 millis
Volt/second, the electrode potential of polarization curve is relative to the electrode potential of standard reversible hydrogen electrode.
From polarization curve, porous carbon manufactured in the present embodiment loads molybdenum disulfide nano sheet composite in electrolysis water
In hydrogen manufacturing experiment, the overpotential when current density is 10 milliamps per square centimeter is 172 millivolts, and this overpotential is significantly lower than
Other same type catalyst.This show prepared by this example porous carbon load molybdenum disulfide nano sheet composite have it is excellent
Water electrolysis hydrogen production catalytic performance.
Embodiment 2, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite, difference are prepared according to method same as Example 1
For：Porous carbon and molybdenum source mass ratio are changed to 12：10 (porous carbon be 60 milligrams, ammonium molybdate be 50 milligrams, deionized water be 5 milli
Rise).In gained composite, the average grain diameter of molybdenum disulfide nano sheet is 4.0 nanometers ± 0.5 nanometer, and the number of plies is 1-3 layers, matter
It is 20.2% to measure percentage composition.
Embodiment 3, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite, difference are prepared according to method same as Example 1
For：Porous carbon and molybdenum source mass ratio are changed to 12：20 (porous carbon be 60 milligrams, ammonium molybdate be 100 milligrams, deionized water be 5 milli
Rise).In gained composite, the average grain diameter of molybdenum disulfide nano sheet is 5.4 nanometers ± 0.5 nanometer, and the number of plies is 1-3 layers, matter
It is 23.85% to measure percentage composition.
Embodiment 4, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite, difference are prepared according to method same as Example 1
For：Porous carbon and molybdenum source mass ratio are changed to 12：40 (porous carbon be 60 milligrams, ammonium molybdate be 200 milligrams, deionized water be 5 milli
Rise).In gained composite, the average grain diameter of molybdenum disulfide nano sheet is 7.1 nanometers ± 0.5 nanometer, and the number of plies is 1-3 layers, matter
It is 38.45% to measure percentage composition.
Embodiment 5, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite, difference are prepared according to method same as Example 1
For：The vulcanization reaction time was changed into 3 hours from 1 hour, in gained composite, molybdenum disulfide nano sheet and embodiment 1 are basic
Unanimously, performance is suitable with the molybdenum disulfide nano sheet that embodiment 1 is obtained.
Embodiment 6, prepare porous carbon load molybdenum disulfide nano sheet composite
Porous carbon load molybdenum disulfide nano sheet composite, difference are prepared according to method same as Example 1
For：Vulcanization reaction temperature is changed into 500 DEG C or 700 DEG C, gained composite from 600 DEG C, molybdenum disulfide nano sheet is with implementing
Example 1 is basically identical, and water electrolysis hydrogen production performance is suitable with the molybdenum disulfide nano sheet that embodiment 1 is obtained.
Comparative example 1,
Comparative example molybdenum disulfide nano sheet is prepared according to method same as Example 1, difference is：Not by porous
Carbon solution standing adsorption ammonium molybdate, but porous carbon and ammonium molybdate physical grinding are mixed.Transmission electron microscope such as Fig. 7 shines
Shown in piece, gained molybdenum disulfide pattern is stacked and caged, and bad dispersibility, size are uneven.As shown in Figure 7, the sulphur of gained two
Change Mo under the same conditions water electrolysis hydrogen production when, current density be 10 milliamps per square centimeter when overpotential than implement
The overpotential that example 1 obtains the ultra-thin molybdenum disulfide nano sheet of small size is high 70 millivolts.
Comparative example 2,
Water electrolysis hydrogen production experiment is carried out using the business molybdenum disulfide powder of purchase.It will be appreciated from fig. 6 that business molybdenum disulphide powder
There is no water electrolysis hydrogen production catalytic performance substantially during last water electrolysis hydrogen production under the same conditions.
Claims (10)
1. a kind of porous carbon loads the preparation method of molybdenum disulfide nano sheet composite, comprise the following steps：
(1) porous carbon adsorption molybdate is utilized, predecessor is obtained；
(2) under an inert atmosphere, the predecessor is heat-treated；Sulfur vapor is vulcanized with the predecessor through Overheating Treatment
Reaction, you can obtain the porous carbon load molybdenum disulfide nano sheet composite.
2. preparation method according to claim 1, it is characterised in that：In step (1), the porous carbon and the molybdate
Mass ratio be 12：(1~40)；And/or,
In step (1), the molybdate is the one or more in ammonium molybdate, sodium molybdate and potassium molybdate.
3. preparation method according to claim 1 or 2, it is characterised in that：The concrete operations of step (1) are as follows：Will be described
Porous carbon and the molybdate are dispersed in water, and are centrifuged after standing adsorption, are collected solid and are dried in vacuo, obtain the forerunner
Thing.
4. preparation method according to claim 3, it is characterised in that：The porous carbon quality and the volume ratio of water are (30
~120) gram：5 liters；And/or,
The time of the standing adsorption is 12~36 hours；And/or,
The vacuum drying temperature is 50~100 DEG C, and the time is 12~36 hours, and vacuum is -0.05~-0.2 MPa.
5. the preparation method according to any one of claim 1-4, it is characterised in that：In step (2), the heat treatment
Temperature is 500~700 DEG C, and the time is 0.5~3 hour.
6. the preparation method according to any one of claim 1-5, it is characterised in that：In step (2), the sulfur vapor with
The mass ratio of the predecessor is 1：(10~50).
7. the preparation method according to any one of claim 1-6, it is characterised in that：In step (2), the vulcanization reaction
Temperature be 500~700 DEG C, the time be 0.25~3 hour.
8. the preparation method according to any one of claim 1-7, it is characterised in that：Step (2) is in dual temperature area heating furnace
Carry out, concrete operations are as follows：2-1) the direction being passed through along the inert gas, dual temperature area heating furnace is placed in by the predecessor
Downstream, sulphur powder is placed in the upstream of dual temperature area heating furnace；2-2) under the downstream temperature, hot place is carried out to the predecessor
Reason；Under the upstream temperature, sulphur powder is distilled, the sulfur vapor is obtained；While the distillation is carried out, institute is kept
Downstream temperature is stated, it is anti-that the sulfur vapor carries out the vulcanization under the downstream temperature with the predecessor Jing Guo the heat treatment
Should, you can obtain the porous carbon load molybdenum disulfide nano sheet composite.
9. the porous carbon load molybdenum disulfide nano sheet that the preparation method any one of claim 1-8 is prepared is combined
Material.
10. application of the porous carbon load molybdenum disulfide nano sheet composite in water electrolysis hydrogen production described in claim 9.
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