CN109675605A - A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications - Google Patents
A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications Download PDFInfo
- Publication number
- CN109675605A CN109675605A CN201910020492.3A CN201910020492A CN109675605A CN 109675605 A CN109675605 A CN 109675605A CN 201910020492 A CN201910020492 A CN 201910020492A CN 109675605 A CN109675605 A CN 109675605A
- Authority
- CN
- China
- Prior art keywords
- preparation
- ncs
- liberation
- hydrogen
- dicyandiamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 21
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 18
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 35
- 229910052799 carbon Inorganic materials 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 238000002604 ultrasonography Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 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
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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 discloses a kind of Ni/Co-NCs liberation of hydrogen materials, preparation method and applications.Preparation step of the present invention mainly includes the following steps: first being mixed nickel acetate, cobalt acetate, dicyandiamide and ethyl alcohol, ultrasonic disperse；It puts it into and is evaporated to obtain Ni/Co-C in water-bath2N4H4Mixture；It is put into resistance furnace to calcine under anaerobic, finally obtains Ni/Co-NCs material.Ni/Co-NCs cost of material prepared by the present invention is low, and preparation method is simple, and liberation of hydrogen works well in alkaline solution, is expected to towards industrialization development.
Description
Technical field
The present invention relates to hydrogen energy source technical fields, specifically, are related to a kind of Ni/Co-NCs liberation of hydrogen material, preparation method
And its application.
Background technique
The energy and environment are the main problems that human social is related to.The energy requirement in the whole world 80% at present
From fossil fuel, this will finally lead to the exhaustion of fossil fuel, and its use also leads to serious environmental pollution.From
It is the inexorable trend developed that fossil fuel, which is gradually turned to using the free of contamination non-fossil energy of sustainable development,.Hydrogen is ideal clear
One of clean energy is also the industrial chemicals of weight, is widely paid attention to by countries in the world.Traditional hydrogen manufacturing gas method generally requires to disappear
Consume a large amount of fossil fuel, and a large amount of by-product can be generated simultaneously, thus electrolysis water as hydrogen manufacturing new technology by scientific research people
Member's extensive concern.Water electrolysis hydrogen production has many advantages, such as that easy, pollution is small, product purity is high, but its evolving hydrogen reaction (2H++2e
→H2Or 2H2O+2e→H2+2OH-) there are more serious cathodic polarizations, lead to higher hydrogen manufacturing cost, be not suitable for answering on a large scale
With.The electrocatalytic hydrogen evolution (ElectrocatalyticHydrogen Evolution Reaction, HER) that developed recently gets up
It is considered as the green hydrogen producing technology of great application prospect.This hydrogen producing technology under the effect of the catalyst, can significantly drop
Low overpotential of hydrogen evolution, with low energy consumption, high-efficient, advantages of environment protection.Catalyst based on noble metals such as Pt, Pd not only rises
Beginning overpotential is low, and activity and stability are all fine, are the best catalyst of current Hydrogen Evolution Performance.But these noble metals exist
The content of the earth is lower and expensive, is unfavorable for practical application.A kind of your non-gold suitable for large-scale practical application found
Belong to liberation of hydrogen catalyst into research hotspot.
Base metal liberation of hydrogen catalyst mainly have phosphide based on transition metal such as Mo, W, Fe, Co, Ni, sulfide with
And their alloy etc..Since the content (about 0.00011%) of Mo and W in the earth's crust is far below Fe (6.8%), Co
(0.003%), therefore the content of Ni (0.0089%) develops the electrocatalytic hydrogen evolution catalyst based on Fe, Co, Ni and is more advantageous to
The extensive industrialization of electrocatalytic hydrogen evolution technology.In recent years the electrocatalytic hydrogen evolution catalyst based on Fe, Co, Ni has obtained sending out energetically
Exhibition, is prepared for the catalyst much haveing excellent performance, plays good impetus to electrocatalytic hydrogen evolution technological industrialization.
Summary of the invention
For present catalytic hydrogen evolution problem, the invention proposes a kind of Ni/Co-NCs liberation of hydrogen material and preparation methods, and
And have studied its application in terms of electrocatalytic hydrogen evolution.The alloy catalyst is lower than most catalyst synthesis costs, main
It wants the earth storage level of element all more sufficient, chemical property is improved by the compound action of two kinds of transition metal elements,
And synthetic method is simple.
The present invention provides a kind of preparation method of Ni/Co-NCs liberation of hydrogen material, comprising the following steps: first by nickel acetate,
Cobalt acetate, dicyandiamide and ethyl alcohol mixing, ultrasonic disperse, so that until solution is clarified；Then clear solution is put into water-bath
It is evaporated to obtain Ni/Co-C2N4H4Mixture；Finally by Ni/Co-C2N4H4Mixture is put into resistance furnace and calcines under anaerobic,
Obtain Ni/Co-NCs material.
In the present invention, the molar ratio of nickel acetate and cobalt acetate is 5:1~1:5, the total mole number of nickel acetate and cobalt acetate and
The proportion of the molal quantity of dicyandiamide is 1:5~1:10.
In the present invention, the molar ratio of nickel acetate and cobalt acetate is 3:1~1:3, the total mole number of nickel acetate and cobalt acetate and
The proportion of the molal quantity of dicyandiamide is 1:6~1:8.
In the present invention, the feed ratio of ethyl alcohol and dicyandiamide is 3:1~5:1ml/mmol.
In the present invention, the ultrasonic disperse time is 5~10 minutes.
In the present invention, the temperature of water-bath is 75~95 DEG C.
In the present invention, ventilated body is nitrogen in resistance furnace, and calcination temperature is 800~1000 DEG C, and calcination time is 2~4
Hour.
The present invention provides Ni/Co-NCs liberation of hydrogen material made from the above-mentioned preparation method of one kind.
The present invention further provides a kind of application of above-mentioned Ni/Co-NCs liberation of hydrogen material in electrocatalytic hydrogen evolution reaction.
Application method includes the following steps:
(1) 1mg Ni/Co-NCs liberation of hydrogen material is weighed to be dissolved in the Nation solution of the 100 prepared 0.5wt% of μ L,
Under ultrasound after evenly dispersed half an hour, 12-18 μ L solution is drawn on glass-carbon electrode, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrocatalytic hydrogen evolution of liberation of hydrogen material is measured in alkaline solution.
Compared to the prior art, the beneficial effects of the present invention are:
The Tafel slope and overpotential of the electrode material are low, therefore liberation of hydrogen works well, and the introducing of nonmetalloid is led
Cause having good stability for catalyst.
Using electrocatalytic hydrogen evolution electrode material of the invention in alkaline medium electrolysis water, through with monometallic liberation of hydrogen material
(Co-NCs and Ni-NCs) and the liberation of hydrogen material (Ni/Co-Cs) introduced without nitrogen compare, it is found that liberation of hydrogen effect of the present invention is good
Good, overpotential is low, and cost is relatively low.Wherein, electrocatalysis characteristic test carries out in the potassium hydroxide solution of 1.0M.
In the present invention, the transition metal element of nickel element and cobalt element as the electron structure containing d, its own can lead to
Electronic structure is overregulated to improve electro-chemical activity, and the synergistic effect between them can effectively reduce overpotential of hydrogen evolution.
In addition, can generate very strong coupling between metallic atom and nitrogen-atoms, which enhance the chemical and thermal stability of material.
Detailed description of the invention
Fig. 1 is the Tafel slope figure for the Ni/Co-NCs liberation of hydrogen material that embodiment 1 obtains.
Fig. 2 is the polarization curve for the Ni/Co-NCs liberation of hydrogen material that embodiment 1 obtains.
Specific embodiment
Technical solution of the present invention is further described below with reference to specific embodiment, but the present invention is not limited to
Following embodiments.
Various raw materials used in various embodiments of the present invention are unless otherwise specified commercially available.
Embodiment 1
Nickel acetate 0.5mmol
Cobalt acetate 1.5mmol
Dicyandiamide 16mmol
Ethyl alcohol 50ml
The preparation method preparation of above-mentioned composite material as follows:
0.5mmol nickel acetate, 1.5mmol cobalt acetate and 16mmol dicyandiamide are poured into the beaker equipped with 50ml ethyl alcohol simultaneously
It is stirred solution, and beaker is put into ultrasound 5 minutes in ultrasonic vibration instrument.After seeing in solution without solid particle, placed
It is heated in 80 DEG C of water-bath, until solution is evaporated.Take out Ni/Co-C2N4H4Mixture is simultaneously put into resistance furnace, is passed through
Nitrogen is calcined 2 hours at a high temperature of 800 DEG C, finally obtains Ni/Co-NCs liberation of hydrogen material.
Application Example 1
The Ni/Co-NCs liberation of hydrogen material of embodiment 1 is ground, glassy carbon electrode surface is used to 0.05 μm of aluminium oxide
Grinding is clean, removes residual sample, is rinsed well, dried using second alcohol and water.
(1) match Nation solution 0.5wt% with anhydrous methanol.It weighs 1mgNi/Co-NCs liberation of hydrogen material and is dissolved in 100 μ L
In prepared Nation solution, evenly dispersed two hours under ultrasound.Then the solution is drawn into 12 μ L in glass carbon electricity again
On extremely, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrode material electrocatalytic hydrogen evolution is measured in alkaline solution.Material Tafel slope is 124mV
dec-1, it is 10mA cm in current density-2Overpotential be 358mV.And in the LSV curve and CV after 1000 circle CV tests
LSV curve deviation before test is little, illustrates that the material possesses good stability.
Embodiment 2
Nickel acetate 1.2mmol
Cobalt acetate 0.6mmol
Dicyandiamide 12mmol
Ethyl alcohol 40ml
The preparation method preparation of above-mentioned composite material as follows:
1.2mmol nickel acetate, 0.6mmol cobalt acetate and 12mmol dicyandiamide are poured into the beaker equipped with 40ml ethyl alcohol simultaneously
It is stirred solution, and beaker is put into ultrasound 5 minutes in ultrasonic vibration instrument.After seeing in solution without solid particle, placed
It is heated in 80 DEG C of water-bath, until solution is evaporated.Take out Ni/Co-C2N4H4Mixture is simultaneously put into resistance furnace, is passed through
Nitrogen is calcined 2 hours at a high temperature of 1000 DEG C, finally obtains Ni/Co-NCs liberation of hydrogen material.
Application Example 2
The Ni/Co-NCs liberation of hydrogen material of embodiment 2 is ground, glassy carbon electrode surface is used to 0.05 μm of aluminium oxide
Grinding is clean, removes residual sample, is rinsed well, dried using second alcohol and water.
(1) match Nation solution 0.5wt% with anhydrous methanol.It weighs 1mgNi/Co-NCs liberation of hydrogen material and is dissolved in 100 μ L
In prepared Nation solution, evenly dispersed two hours under ultrasound.Then the solution is drawn into 18 μ L in glass carbon electricity again
On extremely, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrode material electrocatalytic hydrogen evolution is measured in alkaline solution, material Tafel slope is 96mV
dec-1, it is 10mAcm in current density-2Overpotential be 235mV.And in the LSV curve and CV after 1000 circle CV tests
LSV curve deviation before test is little, illustrates that the material possesses good stability.
Embodiment 3
Nickel acetate 1.0mmol
Cobalt acetate 1.75mmol
Dicyandiamide 20mmol
Ethyl alcohol 80ml
The preparation method preparation of above-mentioned composite material as follows:
1.0mmol nickel acetate, 1.75mmol cobalt acetate and 20mmol dicyandiamide are poured into the beaker equipped with 80ml ethyl alcohol
And it is stirred solution, and beaker is put into ultrasound 5 minutes in ultrasonic vibration instrument.After seeing in solution without solid particle, put
It sets and is heated in 80 DEG C of water-bath, until solution is evaporated.Take out Ni/Co-C2N4H4Mixture is simultaneously put into resistance furnace, is led to
Enter nitrogen, is calcined 4 hours at a high temperature of 1000 DEG C, finally obtain Ni/Co-NCs liberation of hydrogen material.
Application Example 3
The Ni/Co-NCs liberation of hydrogen material of embodiment 3 is ground, glassy carbon electrode surface is used to 0.05 μm of aluminium oxide
Grinding is clean, removes residual sample, is rinsed well, dried using second alcohol and water.
(1) match Nation solution 0.5wt% with anhydrous methanol.It weighs 1mg Ni/Co-NCs liberation of hydrogen material and is dissolved in 100 μ L
In prepared Nation solution, evenly dispersed two hours under ultrasound.Then the solution is drawn into 18 μ L in glass carbon electricity again
On extremely, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrode material electrocatalytic hydrogen evolution is measured in alkaline solution, material Tafel slope is 81mV
dec-1, it is 10mA cm in current density-2Overpotential be 199mV.And in the LSV curve and CV after 1000 circle CV tests
LSV curve deviation before test is little, illustrates that the material possesses good stability.
Comparative example 1
Nickel acetate 2.5mmol
Dicyandiamide 20mmol
Ethyl alcohol 60ml
The preparation method preparation of above-mentioned composite material as follows:
2.5mmol nickel acetate and 20mmol dicyandiamide are poured into the beaker equipped with 60ml ethyl alcohol and are stirred solution,
And beaker is put into ultrasound 5 minutes in ultrasonic vibration instrument.After seeing in solution without solid particle, 80 DEG C of water-bath is placed it in
Middle heating, until solution is evaporated.Take out Ni-C2N4H4Mixture is simultaneously put into resistance furnace, is passed through nitrogen, in 800 DEG C of high temperature
Lower calcining 2 hours, finally obtains Ni-NCs liberation of hydrogen material.
Comparison study example 1
The Ni-NCs liberation of hydrogen material of comparative example 1 is ground, glassy carbon electrode surface is ground using 0.05 μm of aluminium oxide
Mill is clean, removes residual sample, is rinsed well, dried using second alcohol and water.
(1) match Nation solution 0.5wt% with anhydrous methanol.It weighs 1mg Ni-NCs liberation of hydrogen material and is dissolved in 100 μ L and match
In the Nation solution made, evenly dispersed two hours under ultrasound.Then the solution is drawn into 18 μ L in glass-carbon electrode again
On, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrode material electrocatalytic hydrogen evolution is measured in alkaline solution, material Tafel slope is 169mV
dec-1, it is 10mA cm in current density-2Overpotential be 427mV.And in the LSV curve and CV after 1000 circle CV tests
LSV curve before test generates certain deviation, illustrates that the material possesses certain stability.
Comparative example 2
Nickel acetate 2.5mmol
Cobalt acetate 2.5mmol
Ethyl alcohol 60ml
The preparation method preparation of above-mentioned composite material as follows:
2.5mmol nickel acetate and 2.5mmol cobalt acetate are poured into the beaker equipped with 60ml ethyl alcohol and are stirred solution,
And beaker is put into ultrasound 5 minutes in ultrasonic vibration instrument.After seeing in solution without solid particle, 80 DEG C of water-bath is placed it in
Middle heating, until solution is evaporated.Take out Ni/Co-C2H4OH mixture is simultaneously put into resistance furnace, is passed through argon gas, at 800 DEG C
It is calcined 2 hours under high temperature, finally obtains Ni/Co-Cs liberation of hydrogen material.
Comparison study example 2
The Ni/Co-Cs liberation of hydrogen material of comparative example 1 is ground, glassy carbon electrode surface is used to 0.05 μm of aluminium oxide
Grinding is clean, removes residual sample, is rinsed well, dried using second alcohol and water.
(1) match Nation solution 0.5wt% with anhydrous methanol.It weighs 1mg Ni/Co-Cs liberation of hydrogen material and is dissolved in 100 μ L
In prepared Nation solution, evenly dispersed two hours under ultrasound.Then the solution is drawn into 18 μ L in glass carbon electricity again
On extremely, naturally dry.
(2) electrolyte of the potassium hydroxide solution of 1.0M as electro-catalysis is prepared, nitrogen is passed through and throws out air, with 1.0M's
Potassium hydroxide solution cleans the electrode surface of glass-carbon electrode, and glass-carbon electrode, Ag/AgCl electrode, platinum electrode are then connected electrification
Work station is learned, the performance of the electrode material electrocatalytic hydrogen evolution is measured in alkaline solution, material Tafel slope is 141mV
dec-1, it is 10mA cm in current density-2Overpotential be 288mV.And in the LSV curve and CV after 1000 circle CV tests
LSV curve before test generates certain deviation, illustrates that the material possesses certain stability.
Claims (9)
1. a kind of preparation method of Ni/Co-NCs liberation of hydrogen material, which comprises the following steps: first by nickel acetate, vinegar
Sour cobalt, dicyandiamide and ethyl alcohol mixing, ultrasonic disperse, so that until solution is clarified；Then clear solution is put into water-bath and is steamed
It is dry to obtain Ni/Co-C2N4H4Mixture；Finally by Ni/Co-C2N4H4Mixture is put into resistance furnace and calcines under anaerobic, obtains
To Ni/Co-NCs material.
2. preparation method according to claim 1, which is characterized in that the molar ratio of nickel acetate and cobalt acetate is 5:1~1:
5, the proportion of the molal quantity of the total mole number and dicyandiamide of nickel acetate and cobalt acetate is 1:5~1:10.
3. preparation method according to claim 1, which is characterized in that the molar ratio of nickel acetate and cobalt acetate is 3:1~1:
3, the proportion of the molal quantity of the total mole number and dicyandiamide of nickel acetate and cobalt acetate is 1:6~1:8.
4. preparation method according to claim 1, which is characterized in that the feed ratio of ethyl alcohol and dicyandiamide is 3:1~5:
1ml/mmol。
5. preparation method according to claim 1, which is characterized in that the ultrasonic disperse time is 5~10 minutes.
6. preparation method according to claim 1, which is characterized in that the temperature of water-bath is 75~95 DEG C.
7. preparation method according to claim 1, which is characterized in that ventilated body is nitrogen, calcination temperature in resistance furnace
It is 800~1000 DEG C, calcination time is 2~4 hours.
8. it is a kind of according to claim 1~one of 7 described in Ni/Co-NCs liberation of hydrogen material made from preparation method.
9. a kind of application of Ni/Co-NCs liberation of hydrogen material according to claim 8 in electrocatalytic hydrogen evolution reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910020492.3A CN109675605A (en) | 2019-01-09 | 2019-01-09 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910020492.3A CN109675605A (en) | 2019-01-09 | 2019-01-09 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109675605A true CN109675605A (en) | 2019-04-26 |
Family
ID=66192218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910020492.3A Pending CN109675605A (en) | 2019-01-09 | 2019-01-09 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109675605A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975922A (en) * | 2019-12-31 | 2020-04-10 | 上海应用技术大学 | Co @ FePx-NCs material for hydrogen evolution of alkaline solution and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641739A (en) * | 2011-02-22 | 2012-08-22 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with concentration of alkaline metal and active metal components being in gradient distribution and preparation method thereof |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
| CN105833871A (en) * | 2016-04-21 | 2016-08-10 | 长春吉大附中实验学校 | Defect-rich cobalt-inlaid carbon nano tube as well as preparation method and application thereof |
| CN106048650A (en) * | 2016-08-04 | 2016-10-26 | 浙江大学 | 3D porous electrode preparation method and use of 3D porous electrode in electrochemical hydrogen evolution |
| CN107118477A (en) * | 2017-05-12 | 2017-09-01 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN108411324A (en) * | 2018-03-29 | 2018-08-17 | 华南理工大学 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
| CN108821245A (en) * | 2018-06-20 | 2018-11-16 | 湖北大学 | CoxNi0.85-xThe preparation method and applications of Se daltonide |
-
2019
- 2019-01-09 CN CN201910020492.3A patent/CN109675605A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641739A (en) * | 2011-02-22 | 2012-08-22 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with concentration of alkaline metal and active metal components being in gradient distribution and preparation method thereof |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
| CN105833871A (en) * | 2016-04-21 | 2016-08-10 | 长春吉大附中实验学校 | Defect-rich cobalt-inlaid carbon nano tube as well as preparation method and application thereof |
| CN106048650A (en) * | 2016-08-04 | 2016-10-26 | 浙江大学 | 3D porous electrode preparation method and use of 3D porous electrode in electrochemical hydrogen evolution |
| CN107118477A (en) * | 2017-05-12 | 2017-09-01 | 合肥工业大学 | A kind of carbon-coated metallic nano-particles load pvdf membrane and its preparation method and application |
| CN108411324A (en) * | 2018-03-29 | 2018-08-17 | 华南理工大学 | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application |
| CN108821245A (en) * | 2018-06-20 | 2018-11-16 | 湖北大学 | CoxNi0.85-xThe preparation method and applications of Se daltonide |
Non-Patent Citations (2)
| Title |
|---|
| DENG, JIAO ET AL.,: ""Enhanced Electron Penetration through an Ultrathin Graphene Layer for Highly Efficient Catalysis of the Hydrogen Evolution Reaction"", 《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 * |
| ZHANG, SUYUN ET AL.,: ""Cobalt encapsulated N-doped defect-rich carbon nanotube as pH universal hydrogen evolution electrocatalyst"", 《APPLIED SURFACE SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110975922A (en) * | 2019-12-31 | 2020-04-10 | 上海应用技术大学 | Co @ FePx-NCs material for hydrogen evolution of alkaline solution and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108543545B (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
| CN109174162B (en) | Iron-doped bimetallic phosphide electrocatalyst and preparation method and application thereof | |
| CN107376958B (en) | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof | |
| CN108325565B (en) | Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application | |
| CN109569683B (en) | Preparation method and application of nitrogen-phosphorus-codoped porous carbon sheet/transition metal phosphide composite material | |
| CN107587161B (en) | A kind of preparation method of rodlike NiFeSe/C electrolysis water catalyst | |
| CN110743603B (en) | Cobalt-iron bimetal nitride composite electrocatalyst and preparation method and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN104971727B (en) | A kind of preparation method of Ni-based catalyst for hydrogen production from methane vapor reforming | |
| CN107761128B (en) | A kind of FeNiNC electrode material, preparation method and applications | |
| EP2857554A1 (en) | Electrochemical reactor and method for production of fuel gas | |
| CN108212157B (en) | Metal boride water cracking catalyst, preparation method and application thereof in aspect of electrocatalytic water cracking | |
| CN110127655B (en) | Method for preparing biomass carbon-loaded cobalt phosphide electrode material by one-step calcination method | |
| CN110721713B (en) | Mo 2 C catalytic material and preparation method and application thereof | |
| CN111270263B (en) | Cobaltosic oxide electrode with foam nickel loaded with rich boron and oxygen vacancies and preparation method thereof | |
| CN108636428A (en) | A kind of preparation method of metal telluride as two-functional electrolytic catalyst | |
| CN110071299A (en) | Dilval/nitrogen-doped carbon elctro-catalyst preparation and in the application that can be filled in zinc and air cell | |
| CN108704663A (en) | A kind of preparation method of the nano combined electrocatalysis material of bimetallic carbon | |
| CN110904468B (en) | Cerium-doped tungsten phosphide submicron sphere composite material and preparation method and application thereof | |
| CN109759066B (en) | Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst | |
| CN109482214A (en) | The catalyst and preparation method of a kind of graphene-supported ruthenium metal and application | |
| CN110197909A (en) | Ferronickel catalysis material, preparation method and the application in water electrolysis hydrogen production gas, preparation liquid sun fuel | |
| CN110302799B (en) | Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method thereof | |
| CN111206271A (en) | Preparation method, product and application of self-supporting metal doped iron nitride electrode | |
| Saha et al. | Ni 3 Co/G alloy as an earth-abundant robust and stable electrocatalyst for the hydrogen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190426 |