CN109499600A - A kind of bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, preparation method and applications - Google Patents
A kind of bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, preparation method and applications Download PDFInfo
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- CN109499600A CN109499600A CN201811535605.5A CN201811535605A CN109499600A CN 109499600 A CN109499600 A CN 109499600A CN 201811535605 A CN201811535605 A CN 201811535605A CN 109499600 A CN109499600 A CN 109499600A
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- doped carbon
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- molybdenum disulfide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 73
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims abstract description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000013066 combination product Substances 0.000 claims description 2
- 229940127555 combination product Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000002791 soaking Methods 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
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 239000000843 powder Substances 0.000 description 10
- 229910052961 molybdenite Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910007566 Zn-MOF Inorganic materials 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
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Abstract
The present invention relates to a kind bimetallic nitrogen-doped carbon/compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent of molybdenum disulfide and preparation method thereof, it comprises the following specific steps that: 1) preparation of bimetallic nitrogen-doped carbon: using anhydrous methanol as solvent, the mixed solution of zinc salt, cobalt salt, methylimidazole is prepared, bimetallic organic backbone is made；After high-temperature calcination, bimetallic nitrogen-doped carbon is made；2) hydro-thermal method prepares bimetallic nitrogen-doped carbon/molybdenum disulfide composite material: using deionized water as solvent, prepare the mixed solution of four molybdic acid hydrate sodium, thiocarbamide, it is placed in polytetrafluoroethylene (PTFE) autoclave together with bimetallic nitrogen-doped carbon and carries out hydro-thermal reaction, bimetallic nitrogen-doped carbon/molybdenum disulfide composite material is made.The present invention has the advantages that showing excellent catalytic activity and good stability, and preparation cost is cheap when composite material prepared by the present invention is reacted for electrocatalytic hydrogen evolution, repeatability is high, has a extensive future.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution technical field, in particular to a kind of bimetallic nitrogen-doped carbon/molybdenum disulfide is compound
Electrocatalyst materials, preparation method and applications.
Background technique
Since the whole world is continuously increased energy consumption demand, combustion of fossil fuels is that exploitation is clear to consequence caused by environment
Clean energy technology brings huge stimulation, and water electrolysis hydrogen production is one of the effective way for replacing conventional fossil fuel.Electricity is urged
Changing evolving hydrogen reaction (HER) to use platinum or other noble metals as elctro-catalyst is considered as the sustainable and effective hydrogen manufacturing side of one kind
Method, and their large-scale application is limited using scarcity and high-cost noble metal are seriously significant.In recent years, transition metal
Sulfide has been demonstrated potential noble metal can be replaced for HER, these materials not only have the catalytic activity close to platinum, Er Qieke
The more active sites of exposure.Wherein, molybdenum disulfide (MoS2) there is unique two-dimensional layered structure, wherein Mo and S is former
Son is connected to form S-Mo-S interlayer by weak Van der Waals force, the study found that MoS2Catalytic activity mostly come from the side S-Mo
Edge rather than basal plane.However, MoS2There are two disadvantages in HER performance applications: i) under Van der Waals force interaction, MoS2
Nanometer sheet Severe aggregation significantly reduces active site quantity；Ii) 2H-MoS2Since the bad electric conductivity of itself is very big
Ground limits electron transfer capacity.Therefore.MoS2Also there is a big difference for distance practical electro-catalysis application, to MoS2Carry out it is compound with
Improve its performance the research hotspot as the field.
To solve the above problems, by MoS2Catalytic activity, high conductivity can be improved in conjunction with multidimensional structure conduction template
Carbon-based material includes carbon nanotube, carbon nano-fiber, carbon cloth and graphene etc., these materials can effectively facilitate active site electronics
Transfer accelerates electrode reaction dynamics and HER catalytic activity.Bimetallic organic backbone (MOF) be a kind of structure is changeable, pattern can
Control, component diversification and porous new function material, derivative bimetallic nitrogen-doped carbon is by the significant electrode that improves
Electric conductivity, and buffer layer can be served as to prevent MoS2Nanometer sheet stacks.
Therefore, how bimetallic organic backbone derivative constructed into compound structure for new residence in conjunction with molybdenum disulfide, in turn
The electrocatalytic hydrogen evolution activity and stability for improving molybdenum disulfide are a current technical problems urgently to be resolved.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of electrocatalytic hydrogen evolution activity height, stability are good, low-cost
Bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, preparation method and applications.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of bimetallic nitrogen-doped carbon/molybdenum disulfide is compound
Electrocatalyst materials, innovative point are: the bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material kernel is
Polyhedron bimetallic nitrogen-doped carbon, shell are the molybdenum disulfide nano sheet at array-like；And combination product morphology controllable, electric conductivity
By force, active site is more；Bimetallic nitrogen-doped carbon is vertically coated on surface by highdensity molybdenum disulfide nano sheet and nucleocapsid is presented
Structure.
A kind of preparation method of above-mentioned bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, innovative point
Be: the preparation method includes the following steps:
The preparation of step 1) metal organic framework: using anhydrous methanol as solvent, the mixing of zinc salt, cobalt salt, methylimidazole is prepared
Solution, the solid matter isolated after being stirred to react are metal organic framework；
The preparation of step 2 bimetallic nitrogen-doped carbon: by the metal organic framework of step 1) preparation in tube furnace under nitrogen atmosphere
High-temperature calcination is carried out, bimetallic nitrogen-doped carbon is made；
Step 3) hydro-thermal method prepares bimetallic nitrogen-doped carbon/molybdenum disulfide composite material: using deionized water as solvent, preparing four water
The mixed solution of sodium molybdate, thiocarbamide is closed, and the mass ratio of four molybdic acid hydrate sodium and thiocarbamide is 1:1.3~1:3；Above-mentioned mixing is molten
Liquid is placed in reaction kettle together with bimetallic nitrogen-doped carbon prepared in step 2 and carries out hydro-thermal reaction, and products therefrom is centrifuged
It collects, and is cleaned with deionized water, it is dry, bimetallic nitrogen-doped carbon/molybdenum disulfide composite material is made.
Further, the concentration of zinc salt and cobalt salt described in step 1) is 5~40 mg/mL, and the concentration of methylimidazole is
50~200 mg/mL.
Further, high-temperature calcination described in step 2, for the gas used for nitrogen, calcination temperature is 600~850oC,
Calcination time is 0.5~3 h.
Further, the concentration of four molybdic acid hydrate sodium described in step 3) be 3~6.5 mg/mL, the concentration of thiocarbamide be 4~
19 mg/mL。
Further, the temperature of hydro-thermal reaction described in step 3) is 180~220oC, soaking time are 18~48 h.
A kind of application of above-mentioned bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, innovative point are:
The bimetallic nitrogen-doped carbon/application of the molybdenum disulfide composite electro catalytic agent material as elctro-catalyst in evolving hydrogen reaction.
The present invention has the advantages that
(1) bimetallic nitrogen-doped carbon of the present invention/molybdenum disulfide composite electro catalytic agent material, molybdenum disulfide and bimetallic nitrogen-doped carbon
Compound to form unique core-shell structure, this package structure significantly suppresses the serious accumulation of molybdenum disulfide, is significantly increased
Electro catalytic activity bit number of points, accelerate electrocatalytic reaction dynamic process, final to improve electrocatalytic hydrogen evolution performance；Meanwhile
Synergistic effect between molybdenum disulfide nano sheet and bimetallic nitrogen-doped carbon significantly improves the electric conductivity of electrode, and exposure is more effective
Edge defect active site；
(2) bimetallic nitrogen-doped carbon of the present invention/molybdenum disulfide composite electro catalytic agent material preparation method, by cobalt-based MOF
The middle suitable zinc metal of doping, can effectively reduce interface resistance, promotes the transfer in electronically active site, to promote material
HER activity；Meanwhile the bimetallic nitrogen-doped carbon of regular appearance, size uniformity is prepared by changing experimental formula, be conducive to two sulphur
Change molybdenum to grow in its surface compact, securely；And preparation method of the invention is easy to operate, low in cost, repeatability is high, application
It has a extensive future.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is bimetallic nitrogen-doped carbon, pure molybdenum disulfide and bimetallic nitrogen-doped carbon/curing prepared by embodiment 3
The X-ray diffraction spectrogram of molybdenum composite material.
Fig. 2 be embodiment 3 prepared by a) bimetallic nitrogen-doped carbon, b) pure molybdenum disulfide and c) bimetallic nitrogen-doped carbon/
The stereoscan photograph of molybdenum disulfide composite material.
Fig. 3 is bimetallic nitrogen-doped carbon, pure molybdenum disulfide and bimetallic nitrogen-doped carbon/curing prepared by embodiment 3
Molybdenum composite material is in 0.5 M H2SO4Polarization curve in solution.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment 1
The preparation of step 1) metal organic framework: taking 873 mg cobalt nitrates to be dispersed in 30 mL anhydrous methanols, 985.2 mg diformazans
Base imidazoles is dispersed in 10 mL anhydrous methanols, and 1 h is stirred at room temperature after above two solution is mixed, and separates solid, and metal is made
Organic backbone Co-MOF.
Co-MOF powder obtained by step 2 is packed into porcelain boat, is transferred in temperature programming tube furnace, under nitrogen protection, with 1oC/min is warming up to 600oC simultaneously keeps the temperature 3 h；After naturally cool to obtaining black powder, the as metal-doped carbon of cobalt after room temperature
(Co/NC).
Step 3) hydro-thermal method prepares the metal-doped carbon of cobalt/molybdenum disulfide composite material: take 120 mg, tetra- molybdic acid hydrate sodium and
250 mg thiocarbamides are dissolved in 25 mL deionized waters, and solution is poured into 50 mL reaction kettles, are added prepared by 50 mg step 2
The metal-doped carbon of cobalt, be uniformly mixed, sealing.210o18 h of C hydro-thermal reaction, cooled to room temperature, suction filtration are produced
Object is cleaned with deionized water, dry, and the metal-doped carbon of cobalt/molybdenum disulfide composite material (Co/NC MoS is made2).
Embodiment 2
The preparation of step 1) metal organic framework: 150 mg zinc nitrates and 1365 mg cobalt nitrates are taken to be dispersed in 30 mL anhydrous methanols
In, 1980 mg methylimidazoles are dispersed in 10 mL anhydrous methanols, 1 h is stirred at room temperature after above two solution is mixed, from
The heart is collected, and for several times, bimetallic organic backbone ZnCo-MOF-1 is made in washing.
ZnCo-MOF-1 powder obtained by step 2 is packed into porcelain boat, is transferred in temperature programming tube furnace, under nitrogen protection,
With 1oC/min is warming up to 700oC simultaneously keeps the temperature 1 h.After naturally cool to obtaining black powder, as bimetal-doped after room temperature
Nitrogen carbon (ZnCo/NC-1).
Step 3) hydro-thermal method prepares bimetallic nitrogen-doped carbon/molybdenum disulfide composite material: taking 120 mg, tetra- molybdic acid hydrate sodium
It is dissolved in 25 mL deionized waters with 250 mg thiocarbamides, solution is poured into 50 mL reaction kettles, it is made to add 50 mg step 2
Standby bimetal-doped carbon is uniformly mixed, sealing.200o24 h of C hydro-thermal reaction, cooled to room temperature, suction filtration are produced
Object is cleaned with deionized water, dry, and bimetal-doped carbon/molybdenum disulfide composite material (ZnCo/NC-1 MoS is made2).
Embodiment 3
The preparation of step 1) metal organic framework: 223.1 mg zinc nitrates and 654.8 mg cobalt nitrates are taken to be dispersed in 30 mL anhydrous
In methanol, 985.2 mg methylimidazoles are dispersed in 10 mL anhydrous methanols, are stirred at room temperature 1 after above two solution is mixed
H is collected by centrifugation, and for several times, bimetallic organic backbone ZnCo-MOF-2 is made in washing.
ZnCo-MOF-2 powder obtained by step 2 is packed into porcelain boat, is transferred in temperature programming tube furnace, under nitrogen protection,
With 1oC/min is warming up to 700oC simultaneously keeps the temperature 2 h.After naturally cool to obtaining black powder, as bimetal-doped after room temperature
Carbon (ZnCo/NC-2).
Step 3) hydro-thermal method prepares bimetal-doped carbon/molybdenum disulfide composite material: take 120 mg, tetra- molybdic acid hydrate sodium and
250 mg thiocarbamides are dissolved in 25 mL deionized waters, and solution is poured into 50 mL reaction kettles, are added prepared by 50 mg step 2
Bimetal-doped carbon, be uniformly mixed, sealing.200o24 h of C hydro-thermal reaction, cooled to room temperature, suction filtration are produced
Object is cleaned with deionized water, dry, and bimetal-doped carbon/molybdenum disulfide composite material (ZnCo/NC-2 MoS is made2).
Embodiment 4
The preparation of step 1) metal organic framework: 446.2 mg zinc nitrates and 436.5 mg cobalt nitrates are taken to be dispersed in 30 mL anhydrous
In methanol, 985.2 mg methylimidazoles are dispersed in 10 mL anhydrous methanols, are stirred at room temperature 1 after above two solution is mixed
Washing is collected by centrifugation in h, and bimetallic organic backbone ZnCo-MOF-3 is made.
ZnCo-MOF-3 powder obtained by step 2 is packed into porcelain boat, is transferred in temperature programming tube furnace, under nitrogen protection,
With 1oC/min is warming up to 700oC simultaneously keeps the temperature 2 h.After naturally cool to obtaining black powder, as bimetal-doped after room temperature
Carbon (ZnCo/NC-3).
Step 3) hydro-thermal method prepares bimetal-doped carbon/molybdenum disulfide composite material: take 120 mg, tetra- molybdic acid hydrate sodium and
250 mg thiocarbamides are dissolved in 25 mL deionized waters, and solution is poured into 50 mL reaction kettles, are added prepared by 50 mg step 2
Bimetallic nitrogen-doped carbon, be uniformly mixed, sealing.200o24 h of C hydro-thermal reaction, cooled to room temperature, suction filtration are produced
Object is cleaned with deionized water, dry, and bimetallic nitrogen-doped carbon/molybdenum disulfide composite material (ZnCo/NC-3 MoS is made2).
Embodiment 5
The preparation of step 1) metal organic framework: 892.4 mg zinc nitrates are taken to be dispersed in 30 mL anhydrous methanols, 985.2 mg
Methylimidazole is dispersed in 10 mL anhydrous methanols, and 1 h is stirred at room temperature after above two solution is mixed, is collected by centrifugation, and is washed
For several times, metal organic framework Zn-MOF is made.
Zn-MOF powder obtained by step 2 is packed into porcelain boat, is transferred in temperature programming tube furnace, under nitrogen protection, with 1oC/min is warming up to 800oC simultaneously keeps the temperature 2 h.After naturally cool to obtaining black powder, as zinc metal nitrogen-doped carbon after room temperature
(Zn/NC).
Step 3) hydro-thermal method prepares zinc metal nitrogen-doped carbon/molybdenum disulfide composite material: taking 120 mg, tetra- molybdic acid hydrate sodium
It is dissolved in 25 mL deionized waters with 250 mg thiocarbamides, solution is poured into 50 mL reaction kettles, it is made to add 50 mg step 2
Standby zinc metal nitrogen-doped carbon is uniformly mixed, sealing.200o24 h of C hydro-thermal reaction, cooled to room temperature, suction filtration obtain
Product is cleaned with deionized water, dry, and zinc metal nitrogen-doped carbon/molybdenum disulfide composite material (Zn/NC MoS is made2).
The nitrogen-doped carbon of bimetallic prepared by embodiment 3/molybdenum disulfide composite material characterization and electro catalytic activity are tested
Analysis:
As shown in Figure 1, the nitrogen-doped carbon of bimetallic prepared by embodiment 3/molybdenum disulfide composite material (ZnCo/NC-2@MoS2)
X-ray diffraction spectrogram in, the characteristic peak containing metallic cobalt, graphitic carbon and molybdenum disulfide, and the diffraction maximum of molybdenum disulfide is weaker,
This shows that the molybdenum disulfide of stratiform forms lesser stacking.Since the content of zinc metal in composite material is very low, in diffraction spectra
It is not easy to find out in figure.
As shown in Fig. 2, bimetallic nitrogen-doped carbon prepared by embodiment 3 be granatohedron, surface more it is coarse simultaneously
There are recess；Pure molybdenum disulfide is the flower-like microsphere seriously accumulated；Bimetallic nitrogen-doped carbon/molybdenum disulfide composite material (ZnCo/
NC-2@ MoS2) in molybdenum disulfide nano sheet be densely grown in the surface of bimetallic nitrogen-doped carbon, to be formed unique
Core-shell structure.
As shown in figure 3, the nitrogen-doped carbon of bimetallic prepared by embodiment 3/molybdenum disulfide composite material is in 0.5 M H2SO4
There is excellent electrocatalytic hydrogen evolution performance in solution.In five embodiments, embodiment 3(ZnCo/NC-2@MoS2) liberation of hydrogen
Can be best, current density is 10 mA cm-2When overpotential be 130 mV, be much better than pure MoS2485 mV.Other four realities
The overpotential for applying example is respectively as follows: 306 mV(embodiments 1), 280 mV(embodiments 2), 195 mV(embodiments 4) and, 380 mV(are real
Apply example 5).Synergistic effect between the unique core-shell structure of composite material and bimetallic nitrogen-doped carbon and molybdenum disulfide makes its performance
Out than pure MoS2Better electrocatalytic hydrogen evolution performance.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (7)
1. a kind of bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, it is characterised in that: the bimetallic N doping
Carbon/molybdenum disulfide composite electro catalytic agent material kernel is polyhedron bimetallic nitrogen-doped carbon, and shell is two sulphur at array-like
Change molybdenum nanometer sheet；And combination product morphology controllable, electric conductivity is strong, and active site is more；Bimetallic nitrogen-doped carbon is by highdensity two
Molybdenum sulfide nanometer sheet is vertically coated on surface and core-shell structure is presented.
2. a kind of preparation method of bimetallic nitrogen-doped carbon described in claim 1/molybdenum disulfide composite electro catalytic agent material,
Be characterized in that: the preparation method includes the following steps:
The preparation of step 1) metal organic framework: using anhydrous methanol as solvent, the mixing of zinc salt, cobalt salt, methylimidazole is prepared
Solution, the solid matter isolated after being stirred to react are metal organic framework；
The preparation of step 2 bimetallic nitrogen-doped carbon: by the metal organic framework of step 1) preparation in tube furnace under nitrogen atmosphere
High-temperature calcination is carried out, bimetallic nitrogen-doped carbon is made；
Step 3) hydro-thermal method prepares bimetallic nitrogen-doped carbon/molybdenum disulfide composite material: using deionized water as solvent, preparing four water
The mixed solution of sodium molybdate, thiocarbamide is closed, and the mass ratio of four molybdic acid hydrate sodium and thiocarbamide is 1:1.3~1:3；Above-mentioned mixing is molten
Liquid is placed in reaction kettle together with bimetallic nitrogen-doped carbon prepared in step 2 and carries out hydro-thermal reaction, and products therefrom is centrifuged
It collects, and is cleaned with deionized water, it is dry, bimetallic nitrogen-doped carbon/molybdenum disulfide composite material is made.
3. bimetallic nitrogen-doped carbon according to claim 2/molybdenum disulfide composite electro catalytic agent material preparation method,
Be characterized in that: the concentration of zinc salt described in step 1) and cobalt salt is 5~40 mg/mL, and the concentration of methylimidazole is 50~200
mg/mL。
4. bimetallic nitrogen-doped carbon according to claim 2/molybdenum disulfide composite electro catalytic agent material preparation method,
Be characterized in that: high-temperature calcination described in step 2, for the gas used for nitrogen, calcination temperature is 600~850oC, calcination time
For 0.5~3 h.
5. bimetallic nitrogen-doped carbon according to claim 2/molybdenum disulfide composite electro catalytic agent material preparation method,
Be characterized in that: the concentration of four molybdic acid hydrate sodium described in step 3) is 3~6.5 mg/mL, the concentration of thiocarbamide is 4~19 mg/
mL。
6. bimetallic nitrogen-doped carbon according to claim 2/molybdenum disulfide composite electro catalytic agent material preparation method,
Be characterized in that: the temperature of hydro-thermal reaction described in step 3) is 180~220oC, soaking time are 18~48 h.
7. a kind of application of bimetallic nitrogen-doped carbon described in claim 1/molybdenum disulfide composite electro catalytic agent material, feature
It is: the bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material answering in evolving hydrogen reaction as elctro-catalyst
With.
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