CN108385124A - A kind of preparation method of magnesium-yttrium-transition metal/carbon pipe/graphene elctro-catalyst for evolving hydrogen reaction - Google Patents
A kind of preparation method of magnesium-yttrium-transition metal/carbon pipe/graphene elctro-catalyst for evolving hydrogen reaction Download PDFInfo
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- CN108385124A CN108385124A CN201810101088.4A CN201810101088A CN108385124A CN 108385124 A CN108385124 A CN 108385124A CN 201810101088 A CN201810101088 A CN 201810101088A CN 108385124 A CN108385124 A CN 108385124A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 55
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 20
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- -1 graphite alkene Chemical class 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 206010054949 Metaplasia Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
-
- 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
Abstract
The preparation method for magnesium-yttrium-transition metal/carbon pipe/graphene elctro-catalyst that the invention discloses a kind of for evolving hydrogen reaction.Using the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene oxide cladding as presoma, and it is rGO to be heat-treated GO by a step heating, the carbon nanotube that the N that 67@ZIF of ZIF, 8 nano-particle in-situ carburizations are Coated Co nano-particles is adulterated simultaneously, prepares Co@N CNTs@rGO composite materials.The composite material due to its unique three-dimensional hierarchical structure, high porosity, abundant N doping, the high conductivity of rGO and Co nano-particles it is evenly dispersed the advantages that, when its as catalyst for HER when, show excellent electric catalyticing characteristic.Not only electric conductivity is strong for gained composite material of the invention, and active site is more, and electrocatalysis characteristic is good, and prepares raw materials used at low cost, and simple for process, energy consumption of reaction is low, it can be achieved that extensive preparation, is a kind of novel HER elctro-catalysts preparation method of high-efficiency and economic.
Description
Technical field
The invention belongs to material, energy technology fields, and in particular to and a kind of magnesium-yttrium-transition metal for efficient evolving hydrogen reaction/
Carbon nano tube/graphene three-dimensional hierarchical composite material elctro-catalyst and preparation method thereof.
Background technology
It is highlighted with the increasingly serious and energy deficiency of environmental problem, development green, sustainable energy conversion
Become the center of numerous researcher researchs at present with memory technology.Hydrogen is due to calorific value height, the advantages that environment friendly
As a focus of scientific circles' concern.Electrolysis aquatic products hydrogen particularly attracts people's attention since its is efficient, convenient, environmentally friendly.However it is electric
Solution water cathode reaction is related to the proton couple electronic transfer process of multistep, and thermodynamics of reactions and dynamics are slower, cause
Electrolysis water evolving hydrogen reaction（HER）During need higher overpotential.Therefore to solve this problem, there is an urgent need for us
A kind of novel elctro-catalyst is developed, for reducing reaction energy barrier and improves reaction rate.Platinum group metal is HER electro-catalysis at present
Most effective one kind in agent, but since Pt is limited in the deposit of nature, cost is higher seriously to hinder them in business electricity
Solve the extensive use in liquid.
Therefore, in recent years in order to find the method for substituting noble metal HER catalyst, researcher has also carried out largely grinding
Study carefully, such as 3d magnesium-yttrium-transition metals（Fe、Co、Ni）And its corresponding compound such as sulfide, phosphide etc..Among these, special transition
Because of its its unique structure and composition, relatively low metal disappears the hybrid composite material that the carbon base body of race's metal and N doping is formed
Consumption, makes it be concerned in HER.Nevertheless, these hybrid composite materials also face some problems, for example preparation process is numerous
It is trivial, expensive, metal particle size is larger, bad dispersibility, the shortcomings of easily reuniting, so as to cause catalytic activity and stability
It reduces, therefore urgently develops novel economical and efficient electrolysis water HER elctro-catalysts.
Invention content
In order to overcome above-mentioned prior art defect, the purpose of the present invention is to provide a kind of efficient, low cost, catalytic activity
High, the good magnesium-yttrium-transition metal/carbon pipe/graphene three-dimensional hierarchical composite material elctro-catalyst of stability preparation method.
It is prepared by a kind of magnesium-yttrium-transition metal provided by the invention/carbon pipe/graphene three-dimensional hierarchical composite material elctro-catalyst
Raw material includes：Graphene oxide, zinc salt, cobalt salt, cetyl trimethylammonium bromide（CTAB）, methylimidazole.
A kind of magnesium-yttrium-transition metal/carbon pipe/graphene three-dimensional hierarchical composite material electricity for efficient HER provided by the invention
Catalyst, preparation process include：The nucleocapsid bimetallic organic frame wrapped up using graphene（ZIF-67@ZIF-8@GO）As
Template, under inert atmosphere protection, the synchronous thermal reduction for carrying out GO and the carbonisation of ZIF-67@ZIF-8, in situ to make at high temperature
Standby magnesium-yttrium-transition metal/carbon nano tube/graphene composite material elctro-catalyst Co@[email protected] composite material tool prepared
There are unique three-dimensional hierarchical structure and high-specific surface area, restrained effectively the reunion of transition metal Co nano-particles, make the work of cobalt
Property site is fully exposed；Secondly, which is conducive to the transmission of electronics due to its own excellent electric conductivity, carries
The high electric conductivity of composite material entirety；And there is the material abundant N doping may be implemented preferably to act synergistically, and make this
When composite material is used for evolving hydrogen reaction as catalyst, excellent electric catalyticing characteristic is shown（Respectively 108 mV (1 M KOH
) and 86 mV (0.5 M H2SO4) vs. RHE reach 10 milliamperes of current densities every square centimeter）.
Above-mentioned magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material electricity for efficient evolving hydrogen reaction is urged
Agent（Co@N-CNTs@rGO）Preparation method, the specific steps are：
（1）The cube ZIF-8 templates of composite graphite alkene are prepared using coprecipitation（ZIF-8@GO）：By the Zn of 150 ~ 300 mg
(NO3)2·6H2The CTAB of O and 5 mg are added separately in the graphene oxide suspension of 10 mL, are sufficiently stirred, are mixed
Liquid；The mixed liquor is added in the 2-methylimidazole solution of 40 mL, 30 min are stirred at room temperature, by product centrifugation point
From, it is cleaned 3-4 times with ethanol solution, is finally placed in -50 DEG C of freeze drier, 36 ~ 72 h of freeze-drying, products therefrom
As ZIF-8@GO；
（2）The preparation of the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene package（ZIF-67@ZIF-8@GO）：Weigh 100 mg
The step of（1）Obtained ZIF-8@GO, are dispersed in methanol solution, and 20 min of ultrasound are then added 3 into acquired solution
A certain amount of 2-methylimidazole solution of ml stirs 10 min, obtains mixed liquor；Mixed liquor is then transferred to the high pressure of 100 mL
It in reaction kettle, is positioned in 90 ~ 100 DEG C of insulating box, reacts 12 h, product is centrifuged, uses methanol solution by room temperature cooling
Cleaning 3-4 times；Finally product is placed in -50 DEG C of freeze drier, is freeze-dried 36 ~ 72 h, products therefrom is ZIF-
67@ZIF-8@GO；Wherein：The methanol solution contains 3 mg CTAB and a certain amount of CoCl2·6H2O；
（3）The preparation of magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material（Co@N-CNTs@rGO）：By step
（2）The ZIF-67@ZIF-8@GO prepared are weighed and are placed in porcelain boat in right amount, porcelain boat is put into tube furnace as presoma, are led to
Enter argon gas, 800 ~ 1000 DEG C are heated to the speed of 2 DEG C/min, keeps the temperature 6 h at this temperature to get to Co@N-CNTs@rGO
Composite material.
Co@N-CNTs@rGO composite materials prepared by the present invention can be used in catalytic hydrogen evolution reaction, the specific steps are：It will
The Co@N-CNTs@rGO composite materials of preparation, which load to, is used as working electrode on glass-carbon electrode, electric using calomel electrode as reference
Pole, carbon-point are used as to electrode.Its electrochemistry is tested in 1.0 M KOH solutions of argon gas saturation and the sulfuric acid solution of 0.5 M
Performance.
Advantage of the invention is that：（1）In the Co@N-CNTs@rGO composite materials of preparation, transition metal nanoparticles ruler
It is very little very small（Less than 10 nanometers）, form very strong interface coupling with N-CNTs and act on；（2）Co@N-CNTs@rGO composite woods
Material has unique three-dimensional hierarchical structure and larger specific surface area, its application in terms of electro-catalysis is enable to keep higher
Catalytic activity and excellent stability；（3）It prepares raw material and relates only to zinc nitrate hexahydrate, cobalt chloride hexahydrate, dimethyl miaow
The common reagent such as azoles, graphene, CTAB and methanol, ethyl alcohol, at low cost, product purity is high, and preparation process is simple, is easy to industry
Metaplasia is produced, and can be also extended to the classification of other magnesium-yttrium-transition metals/carbon nano tube/graphene three-dimensional compound by the preparation process of the present invention
The preparation of material elctro-catalyst.
The present invention provides it is a kind of efficiently, low cost, stability is good, the Co@N-CNTs@rGO that are easy to industrialized production are multiple
The preparation method and applications of condensation material.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1（SEM）.Its
In：（a）For low power scanning electron microscope (SEM) photograph,（b）For high power scanning electron microscope (SEM) photograph.
Fig. 2 is the transmission electron microscope picture of the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1（TEM）.Its
In：（a）For low power transmission electron microscope picture,（b）For high-resolution-ration transmission electric-lens figure,（c）For partial enlarged view.
Fig. 3 is the power spectrum elemental analysis figure of the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1（EDS）.
Fig. 4 is the X-ray diffraction energy spectrum analysis figure of the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1
（XRD）.
Fig. 5 is the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1, with 5 millivolts of sweep speeds per second
Linear sweep voltammetry curve graph in 1.0 moles every liter of potassium hydroxide electrolyte.
Fig. 6 is the Co@N-CNTs@rGO composite materials prepared by the embodiment of the present invention 1, with 5 millivolts of sweep speeds per second
Linear sweep voltammetry curve graph in 0.5 mole every liter of sulfuric acid electrolyte.
Specific implementation mode
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.For a further understanding of the present invention, with reference to example and attached drawing, the present invention is further described.
Embodiment 1, Co@N-CNTs@rGO composite material and preparation methods and application, include the following steps：
（1）The cube ZIF-8 templates of composite graphite alkene are prepared using coprecipitation（ZIF-8@GO）：By the Zn of 150 ~ 300 mg
(NO3)2·6H2The CTAB of O and 5 mg are added separately in the graphene oxide suspension of 10 mL, are sufficiently stirred, are mixed
Liquid；The mixed liquor is added in the 2-methylimidazole solution of 40 mL, 30 min are stirred at room temperature, by product centrifugation point
From, it is cleaned 3-4 times with ethanol solution, is finally placed in -50 DEG C of freeze drier, 36 ~ 72 h of freeze-drying, products therefrom
As ZIF-8@GO；
（2）The preparation of the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene package（ZIF-67@ZIF-8@GO）：Weigh 100 mg
The step of（1）Obtained ZIF-8@GO, are dispersed in methanol solution, and 20 min of ultrasound are then added into acquired solution
The 2-methylimidazole solution of 3ml stirs 10 min, obtains mixed liquor；Mixed liquor is then transferred to the reaction under high pressure of 100 mL
It in kettle, is positioned in 90 ~ 100 DEG C of insulating box, reacts 12 h, product is centrifuged, cleaned with methanol solution by room temperature cooling
3-4 times；Finally product is placed in -50 DEG C of freeze drier, is freeze-dried 36 ~ 72 h, products therefrom is ZIF-67@
ZIF-8@GO；Wherein：The methanol solution contains 3 mg CTAB and a certain amount of CoCl2·6H2O；
（3）The preparation of magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material（Co@N-CNTs@rGO）：By step
（2）The ZIF-67@ZIF-8@GO prepared are weighed and are placed in porcelain boat in right amount, porcelain boat is put into tube furnace as presoma, are led to
Enter argon gas, 900 DEG C are heated to the speed of 2 DEG C/min, keeps the temperature 6 h at this temperature to get to Co@N-CNTs@rGO composite woods
Material.
Co@N-CNTs@rGO composite materials prepared by the present invention can be used in catalytic hydrogen evolution reaction, the specific steps are：It will
The composite material of preparation, which loads to, is used as working electrode on glass-carbon electrode, using calomel electrode as reference electrode, carbon-point conduct pair
Electrode.Its chemical property is tested in 1.0 M KOH solutions of argon gas saturation and the sulfuric acid solution of 0.5 M.
The present embodiment has the beneficial effect that：（1）In the Co@N-CNTs@rGO composite materials of preparation, cobalt nano-particle size
It is very small（Less than 10 nm）, form very strong interface coupling with N-CNTs and act on；（2）Co@N-CNTs@rGO composite materials
With unique three-dimensional hierarchical structure and larger specific surface area, so that its application in terms of electro-catalysis is kept higher and urge
Change activity and excellent stability；（3）Prepare raw material relate only to zinc nitrate hexahydrate, cobalt chloride hexahydrate, methylimidazole,
The common reagent such as graphene, CTAB and methanol, ethyl alcohol, at low cost, product purity is high, and preparation process is simple, is easy to industrialize
Production, and the preparation process of the present invention can also be extended to other magnesium-yttrium-transition metals/carbon nano tube/graphene three-dimensional classification composite wood
Expect the preparation of elctro-catalyst.
Embodiment 2, Co@N-CNTs@rGO composite material and preparation methods and application, include the following steps：
（1）The cube ZIF-8 templates of composite graphite alkene are prepared using coprecipitation（ZIF-8@GO）：By the Zn of 300 ~ 400 mg
(NO3)2·6H2The CTAB of O and 5 mg are added separately in the graphene oxide suspension of 10 mL, are sufficiently stirred, are mixed
Liquid；The mixed liquor is added in the 2-methylimidazole solution of 40 mL, 30 min are stirred at room temperature, by product centrifugation point
From, it is cleaned 3-4 times with ethanol solution, is finally placed in -50 DEG C of freeze drier, 36 ~ 72 h of freeze-drying, products therefrom
As ZIF-8@GO；
（2）The preparation of the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene package（ZIF-67@ZIF-8@GO）：Weigh 100 mg
The step of（1）Obtained ZIF-8@GO, are dispersed in the methanol solution of 23 mL, 20 min of ultrasound, then to acquired solution
3 ml of middle addition, the 2-methylimidazole solution of 895 mg stir 10 min, obtain mixed liquor；Mixed liquor is then transferred to 100
It in the autoclave of mL, is positioned in 90 ~ 100 DEG C of insulating box, reacts 12 h, product is centrifuged, used by room temperature cooling
Methanol solution cleans 3-4 times；Finally product is placed in -50 DEG C of freeze drier, is freeze-dried 48 h, products therefrom is
ZIF-67@ZIF-8@GO；Wherein：The methanol solution contains 3 mg CTAB and a certain amount of CoCl2·6H2O；
（3）The preparation of magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material（Co@N-CNTs@rGO）：By step
（2）The ZIF-67@ZIF-8@GO prepared are weighed and are placed in porcelain boat in right amount, porcelain boat is put into tube furnace as presoma, are led to
Enter argon gas, 900 DEG C are heated to the speed of 2 DEG C/min, keeps the temperature 6 h at this temperature to get to Co@N-CNTs@rGO composite woods
Material.
Co@N-CNTs@rGO composite materials prepared by the present invention can be used in catalytic hydrogen evolution reaction, the specific steps are：It will
The composite material of preparation, which loads to, is used as working electrode on glass-carbon electrode, using calomel electrode as reference electrode, carbon-point conduct pair
Electrode.Its chemical property is tested in 1.0 M KOH solutions of argon gas saturation and the sulfuric acid solution of 0.5 M.
The present embodiment has the beneficial effect that：（1）In the Co@N-CNTs@rGO composite materials of preparation, cobalt nano-particle size
It is very small（≤10 nm ）, form very strong interface coupling with N-CNTs and act on；（2）Co@N-CNTs@rGO composite materials have
There are unique three-dimensional hierarchical structure and larger specific surface area, its application in terms of electro-catalysis is enable to keep higher catalysis
Active and excellent stability；（3）It prepares raw material and relates only to zinc nitrate hexahydrate, cobalt chloride hexahydrate, methylimidazole, stone
The common reagent such as black alkene, CTAB and methanol, ethyl alcohol, at low cost, product purity is high, and preparation process is simple, is easy to industrial metaplasia
Production, and the preparation process of the present invention can also be extended to other magnesium-yttrium-transition metals/carbon nano tube/graphene three-dimensional hierarchical composite material
The preparation of elctro-catalyst.
Embodiment 3, Co@N-CNTs@rGO composite material and preparation methods and application, include the following steps：
（1）The cube ZIF-8 templates of composite graphite alkene are prepared using coprecipitation（ZIF-8@GO）：By the Zn of 82.5 mg
(NO3)2·6H2The CTAB of O and 5 mg are added separately in the graphene oxide suspension of 10 mL, are sufficiently stirred, are mixed
Liquid；The mixed liquor is added to 40 mL, in the 2-methylimidazole solution of 2.825 g, 30 min is stirred at room temperature, will produce
Object centrifuges, and is cleaned 3-4 times with ethanol solution, is finally placed in -50 DEG C of freeze drier, is freeze-dried 72 h, gained
Product is ZIF-8@GO；
（2）The preparation of the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene package（ZIF-67@ZIF-8@GO）：Weigh 50 mg
The step of（1）Obtained ZIF-8@GO, are dispersed in the methanol solution of 23 mL, 20 min of ultrasound, then to acquired solution
3 ml of middle addition, a certain amount of 2-methylimidazole solution stir 10 min, obtain mixed liquor；Mixed liquor is then transferred to 100
It in the autoclave of mL, is positioned in 90 ~ 100 DEG C of insulating box, reacts 12 h, product is centrifuged, used by room temperature cooling
Methanol solution cleans 3-4 times；Finally product is placed in -50 DEG C of freeze drier, is freeze-dried 48 h, products therefrom is
ZIF-67@ZIF-8@GO；Wherein：The methanol solution contains 3 mg CTAB and a certain amount of CoCl2·6H2O and
NiCl2·6H2O；
（3）The preparation of magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material（Co@N-CNTs@rGO）：By step
（2）The ZIF-67@ZIF-8@GO prepared are weighed and are placed in porcelain boat in right amount, porcelain boat is put into tube furnace as presoma, are led to
Enter argon gas, 800 ~ 1000 DEG C are heated to the speed of 2 DEG C/min, keeps the temperature 6 h at this temperature to get to Co@N-CNTs@rGO
Composite material.
Co@N-CNTs@rGO composite materials prepared by the present invention can be used in catalytic hydrogen evolution reaction, the specific steps are：It will
The composite material of preparation, which loads to, is used as working electrode on glass-carbon electrode, using calomel electrode as reference electrode, carbon-point conduct pair
Electrode.Its chemical property is tested in 1.0 M KOH solutions of argon gas saturation and the sulfuric acid solution of 0.5 M.
The present embodiment has the beneficial effect that：（1）In the Co@N-CNTs@rGO composite materials of preparation, cobalt nano-particle size
It is very small（Less than 10 nm）, form very strong interface coupling with N-CNTs and act on；（2）Co@N-CNTs@rGO composite materials
With unique three-dimensional hierarchical structure and larger specific surface area, so that its application in terms of electro-catalysis is kept higher and urge
Change activity and excellent stability；（3）Prepare raw material relate only to zinc nitrate hexahydrate, cobalt chloride hexahydrate, methylimidazole,
The common reagent such as graphene, CTAB and methanol, ethyl alcohol, at low cost, product purity is high, and preparation process is simple, is easy to industrialize
Production, and the preparation process of the present invention can also be extended to other magnesium-yttrium-transition metals/carbon nano tube/graphene three-dimensional classification composite wood
Expect the preparation of elctro-catalyst.
Claims (3)
1. a kind of preparation method of magnesium-yttrium-transition metal/carbon pipe/graphene elctro-catalyst for evolving hydrogen reaction, which is characterized in that
The specific steps are：
The cube ZIF-8 templates of composite graphite alkene are prepared using coprecipitation（ZIF-8@GO）：By the Zn of 150 ~ 300 mg
(NO3)2·6H2The CTAB of O and 5 mg are added separately to 10 mL, in the graphene oxide suspension of 4.5 mg/mL, fully stir
It mixes, obtains mixed liquor；The mixed liquor is added in the 2-methylimidazole solution of 50 ~ 100 mL, is stirred at room temperature 30
Min centrifuges product, is cleaned 3-4 times with ethanol solution, is finally placed in -50 DEG C of freeze drier, freeze-drying
36 ~ 72 h, products therefrom are ZIF-8@GO；
The preparation of the nucleocapsid bimetallic zeolite imidazole radicals skeleton of graphene package（ZIF-67@ZIF-8@GO）：Weigh 100 ~ 200
The step of mg（1）Obtained ZIF-8@GO, are dispersed in the methanol solution of 10 ~ 30 mL, 20 min of ultrasound, then to institute
The 2-methylimidazole solution that 2 ~ 5 ml are added in solution is obtained, 10 min is stirred, obtains mixed liquor；Then mixed liquor is transferred to
It in the autoclave of 100 mL, is positioned in 80 ~ 100 DEG C of insulating box, reacts 10 ~ 15 h, room temperature cooling centrifuges product
Separation, is cleaned 3-4 times with methanol solution；Finally product is placed in -50 DEG C of freeze drier, is freeze-dried 36 ~ 72 h, institute
It is ZIF-67@ZIF-8@GO to obtain product；Wherein：The methanol solution contains 2 ~ 10 mg CTAB and 150 ~ 300 mg
CoCl2·6H2O；
The preparation of magnesium-yttrium-transition metal/carbon nano tube/graphene three-dimensional hierarchical composite material（Co@N-CNTs@rGO）：By step（2）
The ZIF-67@ZIF-8@GO prepared are weighed and are placed in porcelain boat in right amount, porcelain boat is put into tube furnace, is passed through as presoma
Argon gas is heated to 800 ~ 1000 DEG C with the speed of 2 DEG C/min, keeps the temperature 6h at this temperature to get compound to Co@N-CNTs@rGO
Material.
2. a kind of Co@N-CNTs@rGO composite materials that the preparation method described in claim 1 obtains.
3. a kind of Co N-CNTs rGO composite materials that preparation method as described in claim 1 obtains are catalyzed in evolving hydrogen reaction
Application in agent.
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