CN109046408A - A kind of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and its preparation method and application - Google Patents
A kind of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and its preparation method and application Download PDFInfo
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- CN109046408A CN109046408A CN201810915648.XA CN201810915648A CN109046408A CN 109046408 A CN109046408 A CN 109046408A CN 201810915648 A CN201810915648 A CN 201810915648A CN 109046408 A CN109046408 A CN 109046408A
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- hydrogen evolution
- evolution reaction
- reaction material
- electrocatalytic activity
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 81
- 239000001257 hydrogen Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 55
- 230000000694 effects Effects 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 239000010941 cobalt Substances 0.000 claims abstract description 57
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 235000013495 cobalt Nutrition 0.000 description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000002131 composite material Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- -1 prevents its reunion Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
-
- 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
-
- 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
-
- 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 invention belongs to water electrolysis hydrogen production fields, and in particular to a kind of preparation method and application of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.The method that the present invention prepares compound Electrocatalytic Activity for Hydrogen Evolution Reaction material specifically: disperse polyvinylpyrrolidone and cabaltous nitrate hexahydrate in deionized water, stirring obtains mixed solution；Water-bath, after calcining in tube furnace, cooled to room temperature, washing obtains cobalt simple substance@three-dimensional nitrogen-doped porous carbon material；The cobalt simple substance@three-dimensional nitrogen-doped porous carbon material of above-mentioned preparation is mixed with phosphorus source, is placed in tube furnace and calcines, by the washing of obtained product, drying, obtains the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon.The present invention uses two-step synthesis method, and preparation method is easily operated, simple possible；It is raw materials used rich reserves, cheap.Compound Electrocatalytic Activity for Hydrogen Evolution Reaction material prepared by the present invention has three-dimensional porous structure, all has excellent electrocatalytic hydrogen evolution performance under acid, neutral, alkaline condition.
Description
Technical field
The invention belongs to water electrolysis hydrogen production fields, and in particular to a kind of preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and answer
With a kind of in particular to compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon and its preparation method and application.
Background technique
With energy crisis and the increasingly exacerbation of environmental pollution, develops green energy resource, solves environmental pollution and energy crisis
Problem is to maintain the primary selection of sustainable development.China's main energy sources are non-renewable fossil fuel, and energy resource structure is single
And the carbon dioxide that fossil fuel discharges during burning is also the arch-criminal for leading to greenhouse effects.Current renewable energy
Mainly there are wind energy, solar energy, biomass energy, Hydrogen Energy etc. in source.Wherein Hydrogen Energy is a kind of generally acknowledged ideal fuels, and fuel value is stone
3 times of oil, it is most important that the combustion product of hydrogen only has water, is a kind of efficient, clean energy.Therefore exploitation Hydrogen Energy is to solve
Current problem most efficient method.
Most efficient electrocatalytic hydrogen evolution reaction (HER) catalyst is still precious metals pt at present, because the reserves of noble metal are dilute
It is few, it is expensive, still it cannot be mass produced and apply.So the base metal HER that exploitation can substitute precious metals pt is urged
Agent is to solve the effective way of this problem.Phosphatization cobalt, which is proved to be a kind of, has high activity HER catalyst, and because of its storage
Amount is abundant and cheap, so it is suitble to large-scale production and application, but monomer phosphatization cobalt is often easy to reunite, is unfavorable for active site
Sufficiently exposure, a kind of available strategy for preventing it from reuniting when by it in conjunction with suitable carbon carrier.For example common carbon carrier has
Graphene and carbon nanotube.Although graphene and carbon nanotube, which can be anchored phosphatization cobalt nanometer particle, prevents its reunion, graphite
The preparation process of alkene is needed using strong oxidizer, such as the concentrated sulfuric acid, potassium permanganate etc., and time-consuming, and preparation condition is harsh and dangerous,
Obtained graphene is also difficult to spread out, these disadvantages limit the commonly used of graphene；The preparation process of carbon nanotube
Complexity hardly results in uniform carbon nanotube.Therefore, the nanoparticle with HER catalytic activity is born using method appropriate
Being loaded in the carbon carrier easily prepared is that improvement monomer is easy to reunite, and solving the preparation of the carbon carriers such as graphene, there are the effective ways of disadvantage.
Currently, some phosphatization cobalts and the compound catalyst of carbon carrier there are phosphatization cobalt nanometer particle size is larger, cause to live
Property site exposure it is insufficient, the overpotential of electrolysis water liberation of hydrogen is higher, wastes electric energy；Stability is poor, is unable to long-term stable work,
Lead to HER inefficiency；What is had can only obtain preferable hydrogen evolution activity not under conditions of acid or alkalinity etc. is more single
It can work under full pH aqueous environment, limit the application range of HER catalyst.In addition, different carbon materials can produce
Raw special effect, such as the doping of nitrogen-atoms can lead to carbon material defect and generate more active sites, to reinforce it
Catalytic activity.
Summary of the invention
It is an object of the invention to overcome technological deficiency existing in the prior art, such as: monomer phosphatization cobalt is easy to reunite, unfavorable
In the abundant exposure of active site；The graphene preparation condition of use is harsh and dangerous, and is difficult to spread out；It hardly results in
One carbon nanotube；Some phosphatization cobalts and the compound catalyst of carbon carrier cause to live there are phosphatization cobalt nanometer particle size is larger
Property site exposure it is insufficient, the overpotential of electrolysis water liberation of hydrogen is higher, waste electric energy, the problems such as stability, poor HER inefficiency,
The present invention provides a kind of preparation methods of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
Specifically, the technical scheme adopted by the invention is as follows:
(1) metal carbon matrix precursor is prepared:
Polyvinylpyrrolidone and cabaltous nitrate hexahydrate are dispersed in deionized water, stirring obtains mixed solution；Water-bath is anti-
It answers, obtains product；After calcining in tube furnace, cooled to room temperature, washing obtains cobalt simple substance@three-dimensional nitrogen and mixes
Miscellaneous porous carbon materials；
(2) phosphatization:
The cobalt simple substance@three-dimensional nitrogen-doped porous carbon material of step (1) is mixed with phosphorus source, is placed in tube furnace and calcines, will obtain
Product washing, dry, obtain the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon.
In step (1), the mass ratio of the cabaltous nitrate hexahydrate and polyvinylpyrrolidone is 0.8-1.4；The stirring
Time is 10min-30min；The bath temperature is 65 DEG C -75 DEG C, and the water bath time is 5h-7h；The calcination temperature is
750 DEG C -800 DEG C, the calcination time is 40min-50min, and heating rate is 5 DEG C of min-1；
In step (2), phosphorus source is red phosphorus；The cobalt simple substance@three-dimensional nitrogen-doped porous carbon material and the mass ratio of phosphorus source are 0.5-
0.7；The calcination temperature is 500 DEG C -600 DEG C, and the calcination time is 1.5h-2.5h, and heating rate is 5 DEG C of min-1；Institute
Stating drying temperature is 80 DEG C.
The present invention also provides a kind of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, the material is in three-dimensional porous carbon nanosheet network knot
Structure, large specific surface area；Phosphatization cobalt nanometer particle is evenly embedded into carbon nanosheet, and phosphatization cobalt particle size is 5-10nm.
The present invention also provides a kind of purposes of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is used for
Electrolysis water liberation of hydrogen.
Compared with prior art compared with beneficial effects of the present invention embody as follows:
(1) for the present invention with polyvinylpyrrolidone (PVP) for carbon source, cabaltous nitrate hexahydrate is cobalt source, raw materials used rich reserves,
It is cheap.Here, polyvinylpyrrolidone, which may act as dispersing agent, makes the dispersion of cobalt nitrate in aqueous solution more evenly, obtain
The cobalt simple substance being reduced is smaller, and particle size is uniform.At high temperature, the gas that the decomposition that the six directions closes cobalt nitrate generates causes
The formation of three-dimensional porous carbon, while cobalt ions is reduced among cobalt simple substance insertion nanometer carbon plate, saves some researchs first
The process of carbon carrier is prepared, finally obtained phosphatization cobalt button diameter only has 5-10nm, exposes more active sites.
(2) in addition, the present invention uses two-step synthesis method, the first step prepares cobalt simple substance@three-dimensional nitrogen-doped porous carbon material, the
Two steps prepare the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon, and preparation method is easily operated, simply may be used
Row.In preparation process of the present invention, the introducing of three-dimensional porous carbon also improves compound while increasing the specific surface area of compound
The electric conductivity of object accelerates the transmission rate of electronics again while exposing more active sites, so the electricity of compound is urged
Changing Hydrogen Evolution Performance is also greatly enhanced.
(3) comparison using graphene, carbon nanotube as the catalyst material of carrier can only small lot prepare, catalysis of the invention
Agent material is easy to produce in enormous quantities, and the phosphatization cobalt ions for being embedded in carbon nanosheet is wrapped up by surrounding carbon, avoids and electrolyte solution
It directly contacts, this is more stable than the exposed catalyst in carbon support.There is the carbon material electric conductivity of nitrogen atom doping also can
It is further improved, to improve liberation of hydrogen efficiency.
(4) the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon prepared by the present invention, phosphatization cobalt nanoparticle
Son is smaller, about 10 nm and is dispersed on carbon nanosheet；With three-dimensional porous structure, ensure that electric in electrolyte solution
The transmission by all kinds of means of son, ion, the doping of nitrogen can optimize carbon material electronic structure, further enhance electro catalytic activity；It is acid,
All there is excellent catalytic performance under neutral, alkaline condition.Compound Electrocatalytic Activity for Hydrogen Evolution Reaction material prepared by the present invention, in full pH model
All there is good electrocatalytic hydrogen evolution performance, in 0.5 M H in enclosing2SO4, in 1.0 M PBS and 1.0 M KOH, when current density reaches
To 10 mA cm-2When, required overpotential of hydrogen evolution is followed successively by 131mV, 300 mV and 180 mV, corresponding Tafel slope according to
Secondary is 58 mV dec-1、71 mV dec-1With 65 mV dec-1。
Detailed description of the invention
Fig. 1 is the XRD diffraction spectrogram of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon of the invention；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon of the invention；
Fig. 3 is the transmission electron microscope figure of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon of the invention
(TEM)；
Fig. 4 is in 0.5 M H2SO4 In, the electro-catalysis of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon is analysed
Hydrogen curve graph；
Fig. 5 is in 0.5 M H2SO4 In, the Ta Feier Xie of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt three-dimensional N doping porous carbon
Rate figure；
Fig. 6 is the electrocatalytic hydrogen evolution of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon in 1.0 M KOH
Curve graph；
Fig. 7 is the Tafel slope of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon in 1.0 M KOH
Figure；
Fig. 8 is the electrocatalytic hydrogen evolution of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon in 1.0 M PBS
Curve graph；
Fig. 9 is the Tafel slope of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon in 1.0 M PBS
Figure.
Specific embodiment
Below with reference to specific example, the invention will be further elaborated:
Embodiment 1:
(1) metal carbon matrix precursor is prepared:
5 grams of polyvinylpyrrolidones are dissolved in 150 milliliters and contain 4 grams of Co (NO3)2·6H2In the deionized water of O, then stir
10 minutes, obtain mixed solution；Then mixed solution is transferred in water-bath and water-bath 5 hours at 65 DEG C, obtains product；
Then place the product in 40min in porcelain crucible, is calcined in 750 DEG C of tube furnace, heating rate is 5 DEG C of min-1, naturally cold
But it is simultaneously washed respectively 3 times with deionized water, ethyl alcohol to after room temperature, collecting products therefrom, it is porous to obtain cobalt simple substance three-dimensional N doping
Carbon material (Co@3D-NPC composite material).
(2) phosphatization:
Co@3D-NPC composite material 0.5g and red phosphorus powder 1g that step (1) obtains are placed in ceramic boat, and by red phosphorus powder
It is placed in upstream side；Then ceramic boat is heated into 1.5h at 500 DEG C in quartz ampoule, protected under nitrogen flowing, heating rate 5
℃·min -1；Finally, stove is cooled to room temperature, obtained black product deionized water and ethyl alcohol are respectively washed 3 times, and
It is dry at 80 DEG C, obtain phosphatization cobalt@three-dimensional N doping porous carbon compound Electrocatalytic Activity for Hydrogen Evolution Reaction material (CoP@3D-NPC composite wood
Material).
Embodiment 2:
(1) metal carbon matrix precursor is prepared
5 grams of polyvinylpyrrolidones are dissolved in 150 milliliters and contain 6 grams of Co (NO3)2·6H2In the deionized water of O, then stir
20 minutes, obtain mixed solution；Then mixed solution is transferred in water-bath and water-bath 6 hours at 70 DEG C, obtains product；
Then place the product in 45min in porcelain crucible, is calcined in 775 DEG C of tube furnace, heating rate is 5 DEG C of min-1, naturally cold
But it is simultaneously washed respectively 3 times with deionized water, ethyl alcohol to after room temperature, collecting products therefrom, it is porous to obtain cobalt simple substance three-dimensional N doping
Carbon material (Co@3D-NPC composite material).
(2) phosphatization:
Co@3D-NPC composite material 0.6g and red phosphorus powder 1g that step (1) obtains are placed in ceramic boat, and by red phosphorus powder
It is placed in upstream side；Then ceramic boat is heated into 2h at 550 DEG C in quartz ampoule, protected under nitrogen flowing, heating rate 5
℃·min -1；Finally, stove is cooled to room temperature, obtained black product deionized water and ethyl alcohol are respectively washed 3 times, and
It is dry at 80 DEG C, obtain phosphatization cobalt@three-dimensional N doping porous carbon compound Electrocatalytic Activity for Hydrogen Evolution Reaction material (CoP@3D-NPC composite wood
Material).
Embodiment 3
(1) metal carbon matrix precursor is prepared:
5 grams of polyvinylpyrrolidones are dissolved in 150 milliliters and contain 7 grams of Co (NO3)2·6H2In the deionized water of O, then stir
30 minutes, obtain mixed solution；Then mixed solution is transferred in water-bath and water-bath 7 hours at 75 DEG C, obtains product；
Then place the product in 50min in porcelain crucible, is calcined in 800 DEG C of tube furnace, heating rate is 5 DEG C of min-1, naturally cold
But it is simultaneously washed respectively 3 times with deionized water, ethyl alcohol to after room temperature, collecting products therefrom, it is porous to obtain cobalt simple substance three-dimensional N doping
Carbon material (Co@3D-NPC composite material).
(2) phosphatization:
Co@3D-NPC composite material 0.7g and red phosphorus powder 1g that step (1) obtains are placed in ceramic boat, and by red phosphorus powder
It is placed in upstream side；Then ceramic boat is heated into 2.5h at 600 DEG C in quartz ampoule, protected under nitrogen flowing, heating rate 5
℃·min -1；Finally, stove is cooled to room temperature, by obtained black product deionized water and ethanol washing 3 times, and in
It is dry at 80 DEG C, obtain the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon (CoP@3D-NPC composite material).
Electrocatalytic hydrogen evolution performance test:
It is tested using electrocatalytic hydrogen evolution performance of the three-electrode system to the embodiment 1-3 Co@3D-NPC composite material prepared.
Working electrode is prepared using drop-coating, the specific process is as follows: 0.98 mL is added in the centrifuge tube of 2 mL in the sample for weighing 5 mg
The Nafion solution that ethyl alcohol and 0.02 mL mass fraction are 5 %, 30 min of ultrasound form catalyst solution.Use diameter for 5
The glassy carbon electrode of mm is working electrode, mirror surface is polished smooth into, by the catalyst solution drop coating of 0.01 ml in working electrode
On, electro-chemical test is carried out after natural drying, and test solution is respectively 0.5 M H2SO4, 1.0 M KOH, 1.0 M PBS.
In 0.5 M H2SO4, in 1.0 M PBS and 1.0 M KOH, when current density reaches 10 mA cm-2When, it is required
Overpotential of hydrogen evolution be followed successively by 131mV, 300 mV and 180 mV, corresponding Tafel slope only has 58 mV dec respectively-1、71
mV dec-1With 65 mV dec-1。
Fig. 1 is that the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon of the invention (is mixed by phosphatization cobalt@3D nitrogen
Miscellaneous porous carbon) XRD diffraction spectrogram, the specially obtained XRD diffraction spectrogram of phosphatization cobalt@3D N doping porous carbon of embodiment 2,
Its main diffraction maximum matches with CoP phase standard card JCPDS:29-0497, shows the success of phosphatization cobalt@3D N doping porous carbon
Preparation.
Fig. 2 is the compound Electrocatalytic Activity for Hydrogen Evolution Reaction scanning of materials electron microscope of phosphatization cobalt@three-dimensional N doping porous carbon of the invention；By scheming
2 can be seen that, it can be seen that phosphatization cobalt 3D N doping porous carbon sample is in three-dimensional porous carbon nanosheet network structure, is possessed larger
Specific surface area.
Fig. 3 is the transmission electron microscopy of the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon of the invention
Mirror figure, it can be seen that CoP nanoparticle is evenly embedded into carbon nanosheet, and phosphatization cobalt particle size is 5-10nm, and lesser partial size has
Conducive to the abundant exposure of active site, to improve electro catalytic activity.
Fig. 4 is in 0.5 M H2SO4 In, the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material (phosphatization of phosphatization cobalt@three-dimensional N doping porous carbon
Cobalt@3D N doping porous carbon) electrocatalytic hydrogen evolution curve graph；As seen from Figure 4, when current density reaches 10 mA cm-2When, institute
The overpotential of hydrogen evolution needed only has 131mV respectively.
Fig. 5 is in 0.5 M H2SO4 In, the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material (phosphatization of phosphatization cobalt@three-dimensional N doping porous carbon
Cobalt@3D N doping porous carbon) Tafel slope figure；As seen from Figure 5, corresponding Tafel slope is 58 mV dec-1。
Fig. 6 is the phosphatization cobalt compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of@three-dimensional N doping porous carbon (the phosphatization cobalt@in 1.0 M KOH
3D N doping porous carbon) electrolysis water liberation of hydrogen curve graph, when current density reaches 10 mA cm-2When, required liberation of hydrogen is excessively electric
There was only 180mV respectively in position.
Fig. 7 is the phosphatization cobalt compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of@three-dimensional N doping porous carbon (the phosphatization cobalt@in 1.0 M KOH
3D N doping porous carbon) Tafel slope figure；As seen from Figure 7, corresponding Tafel slope is 65 mV dec-1。
Fig. 8 is the phosphatization compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of cobalt@three-dimensional N doping porous carbon (phosphatization cobalt@3D in 1.0 M PBS
N doping porous carbon) electrolysis water liberation of hydrogen curve graph, when current density reaches 10 mA cm-2When, required overpotential of hydrogen evolution
There was only 300mV respectively.
Fig. 9 is the phosphatization compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of cobalt@three-dimensional N doping porous carbon (phosphatization cobalt@3D in 1.0 M PBS
N doping porous carbon) Tafel slope figure, corresponding Tafel slope be 71 mV dec-1。
Compound Electrocatalytic Activity for Hydrogen Evolution Reaction material prepared by the present invention, within the scope of full pH, i.e., in acid, neutral, alkaline condition
Under, all there is good electrocatalytic hydrogen evolution performance, in 0.5 M H2SO4, in 1.0 M PBS and 1.0 M KOH, when current density reaches
To 10 mA cm-2When, required overpotential of hydrogen evolution is followed successively by 131mV, 300 mV and 180 mV, corresponding Tafel slope
It is followed successively by 58 mV dec-1、71 mV dec-1With 65 mV dec-1.To sum up, the present invention obtains preparation method and significantly reduces system
The overpotential of hydrogen evolution of standby phosphatization cobalt@three-dimensional N doping porous carbon, improves stability and electrolytic efficiency and solves some urge
The problem of agent can only work in single aqueous environment.
Claims (10)
1. a kind of preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, which comprises the following steps:
(1) metal carbon matrix precursor is prepared:
Polyvinylpyrrolidone and cabaltous nitrate hexahydrate are dispersed in deionized water, stirring obtains mixed solution；Water-bath is anti-
It answers, obtains product；After calcining in tube furnace, cooled to room temperature, washing obtains cobalt simple substance@three-dimensional nitrogen and mixes
Miscellaneous porous carbon materials；
(2) phosphatization:
The cobalt simple substance@three-dimensional nitrogen-doped porous carbon material of step (1) is mixed with phosphorus source, is placed in tube furnace and calcines, will obtain
Product washing, dry, obtain the compound Electrocatalytic Activity for Hydrogen Evolution Reaction material of phosphatization cobalt@three-dimensional N doping porous carbon.
2. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (1), institute
The mass ratio for stating cabaltous nitrate hexahydrate and polyvinylpyrrolidone is 0.8-1.4.
3. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (1), institute
Stating mixing time is 10min-30min；The bath temperature is 65 DEG C -75 DEG C, and the water bath time is 5h-7h.
4. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (1), institute
Stating calcination temperature is 750 DEG C -800 DEG C, and the calcination time is 40min-50min, and heating rate is 5 DEG C of min-1。
5. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (2), institute
Stating phosphorus source is red phosphorus.
6. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (2),
The cobalt simple substance@three-dimensional nitrogen-doped porous carbon material and the mass ratio of phosphorus source are 0.5-0.7.
7. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (2), institute
Stating calcination temperature is 500 DEG C -600 DEG C, and the calcination time is 1.5h-2.5h, and heating rate is 5 DEG C of min-1。
8. the preparation method of compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 1, which is characterized in that in step (2), institute
Stating drying temperature is 80 DEG C.
9. compound Electrocatalytic Activity for Hydrogen Evolution Reaction material prepared by the method as described in claim 1-8 any one, which is characterized in that described
Material is in three-dimensional porous carbon nanosheet network structure, and phosphatization cobalt nanometer particle is evenly embedded into carbon nanosheet, and phosphatization cobalt button diameter is big
Small is 5-10nm.
10. compound Electrocatalytic Activity for Hydrogen Evolution Reaction material according to claim 9 is used for electrolysis water liberation of hydrogen.
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