CN108479839A - A kind of preparation method and applications of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding - Google Patents
A kind of preparation method and applications of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding Download PDFInfo
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- CN108479839A CN108479839A CN201810267860.XA CN201810267860A CN108479839A CN 108479839 A CN108479839 A CN 108479839A CN 201810267860 A CN201810267860 A CN 201810267860A CN 108479839 A CN108479839 A CN 108479839A
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- cobalt
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 30
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000005253 cladding Methods 0.000 title claims abstract description 12
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 108010010803 Gelatin Proteins 0.000 claims abstract description 11
- 229920000159 gelatin Polymers 0.000 claims abstract description 11
- 239000008273 gelatin Substances 0.000 claims abstract description 11
- 235000019322 gelatine Nutrition 0.000 claims abstract description 11
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000012456 homogeneous solution Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract 4
- 238000010348 incorporation Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 229920001690 polydopamine Polymers 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OKZJGWWKRGIIRL-UHFFFAOYSA-N [N].NC1=NC(N)=NC(N)=N1 Chemical compound [N].NC1=NC(N)=NC(N)=N1 OKZJGWWKRGIIRL-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic 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
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of nickel cobalt iron/carbon-nitrogen material of carbon nitrogen compound cladding, including step：(1）Prepare the mixture of nickel containing gelatin, cobalt and ferrous ion ethylenediamine complex compound；（2）Melamine is scattered in formation catalyst precursor 1 in the mixture；(3）Catalyst precursor 1 is pyrolyzed step by step, obtains catalyst precursor 2；(4）It in the surface modification poly-dopamine of catalyst precursor 2, is then pyrolyzed, obtains a kind of nickel cobalt iron/carbon-nitrogen material of carbon nitrogen compound cladding.The present invention first adulterates the ethylenediamine complex compound of nickel, cobalt and ferrous ion into carbon nitrogen composite structure by a certain percentage, and the mutual synergistic effect of these metals also greatly improves the electroactive of catalyst；Substep pyrolysis is used to make nitrogen in a manner of in situ in high efficiency incorporation carbon structure；By forming carbon nitrogen compound protective layer in catalyst particle surface, the stability and electro catalytic activity of catalyst are greatly improved.
Description
Technical field
The invention belongs to model electrochemical field of energy source materials, and in particular to a kind of nickel-of carbon-to-nitrogen compound cladding
The preparation method and applications of cobalt-iron/carbon-to-nitrogen material.
Background technology
Currently, find novel energy environmentally friendly, that meet sustainable development idea receive countries in the world government and
The great attention of scientific and technological work person.Electrochemical energy source technology has complied with this idea of development, so various novel electrifications
The energy is learned by people's extensive concern, in these novel electrochemical energy source technologies, metal-air battery has apparent excellent
Point, should foreground it is very extensive.In these metal-air batteries, the battery of rechargeable type since it can be used repeatedly and
More it is of practical significance.By taking Sodic Magmatism as an example, its positive and negative electrode electrode reaction can be expressed as：
Discharge process：
Cathode：Zn + 4OH- ® Zn(OH-)4 2- +2e
Anode：2H2O + O2 + 4e ® 4OH-
Charging process：
Cathode： Zn(OH-)4 2- +2e ® Zn + 4OH-
Anode： 4OH-® 2H2O + O2+ 4e
I.e. for anode, discharge process and charging process are oxygen and water（OH-）Between mutually convert process, that is, discharge
Process is oxygen reduction reaction（ORR）, and charging process is oxygen evolution reaction（OER）.Smoothly to realize this conversion process, properly
Elctro-catalyst it is extremely important, that is to say, that oxygen and water（OH-）Between electro-catalysis conversion be very crucial step.
In numerous elctro-catalysts, platinum and platinum-base composite material are considered as the best catalyst for being used for oxygen reduction reaction (ORR)；
And the oxide of ruthenium and iridium is the best catalyst of oxygen evolution reaction (OER).However, the either composite material of platinum or platinum, also
It is the oxide of ruthenium and iridium, the of high cost of these materials, durability are poor, and their resources on earth are limited, serious to make
About their practical application.Therefore, high efficiency, low cost and ORR the and OER catalyst with good stability are developed, with
Just precious metal catalyst is substituted, is the work with important actual application value.A large amount of research and technology develops work
Work shows that the carbon-to-nitrogen composite materials of certain base metal doping have excellent physical/chemical, in the new energy of electrochemistry
Source catalytic field has great potential using value.It, can be to wherein adulterating by carbon nano-structured middle carry out N doping
Certain metal nanoparticles play stabilization, it is possible thereby to prepare excellent ORR and OER elctro-catalysts.
Invention content
The object of the present invention is to provide a kind of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding, mesh of the invention
The nickel-cobalt-iron/carbon-to-nitrogen material for additionally providing a kind of carbon-to-nitrogen compound cladding preparation method.
In order to achieve the above objectives, embodiment of the present invention is：A kind of nickel-cobalt-iron/carbon-to-nitrogen of carbon-to-nitrogen compound cladding
The preparation method of material, includes the following steps：
（1）It prepares and contains ferrous acetate (Fe (CH3COO)2×4H2O), nickel acetate (Ni (CH3COO)2×4H2) and cobalt acetate O
(Co(CH3COO)2×4H2O the aqueous solution of salt-mixture) is then slowly added to ethylenediamine into the aqueous solution, stirs at room temperature
It mixes；Gelatin is then added, acquired solution is heated to 50oC is simultaneously stirred, until forming uniform mixture；
In the aqueous solution, nickel ion, ferrous ion and the total content of cobalt ions are 0.5 ~ 5 wt%；In the aqueous solution, nickel
The mass ratio of ion, ferrous ion and cobalt ions is 1:（0.1~0.2）：（0.2~0.8）；The addition of the ethylenediamine be nickel from
3 times of son, ferrous ion and cobalt ions gross mass；The addition of the gelatin is：The mass percent of gelatin in aqueous solution
For 0.5 ~ 10 %；
（2）Melamine is added into said mixture, is sufficiently stirred, melamine is made to be fully dispersed in solution, is formed equal
Even suspension；Then, by the suspension 80oIt is evaporated under C vacuum conditions, the solid matter of formation is 40oIt is dried in vacuo, obtains under C
Catalyst precursor -1；
The addition of the melamine is：The mass percent of melamine in the mixture is 5 ~ 50 %；
（3）Above-mentioned catalyst precursor -1 is transferred in reaction vessel, nitrogen is passed through, with 5oC min-1Speed be warming up to 300oC ~ 500 oC keeps certain time at this temperature；Then, 800 are continuously heating to identical heating rate oC ~ 1000oC keeps certain time at this temperature；Subsequent cooled to room temperature, obtains catalyst precursor -2；
（4）Isopropyl alcohol and water is pressed 1:2 volume ratios form mixed solvent, are then added three（Methylol）Aminomethane fully stirs
Homogeneous solution is formed after mixing, and makes three（Methylol）The quality (g) of aminomethane and mixed solvent:Volume (mL)=1:1000；Then
Above-mentioned catalyst precursor -2 is added in the homogeneous solution, after gained mixture is ultrasonically treated, adds dopamine, is continued
It is sufficiently stirred at room temperature；Mixture is filtered later, is washed, obtained solid is 40oThe vacuum drying of C, before obtaining catalyst
Drive body -3；
The quality (g) of the catalyst precursor -2 and homogeneous solution:Volume (mL)=1:500；Dopamine and complex catalyst precursor
The mass ratio of body -2 is（0.2 ~ 10）:1；
（5）Above-mentioned catalyst precursor -3 is transferred in reaction vessel, nitrogen is passed through, with 5oC min-1Speed be warming up to 850oC is kept certain time at this temperature, and subsequent cooled to room temperature obtains catalyst.
A kind of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding prepared by the method is to oxygen reduction reaction
（ORR）Electro catalytic activity and to oxygen evolution reaction（OER）Electro catalytic activity test in terms of application.
A kind of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding prepared by the present invention, takes full advantage of base metal and mixes
The active invigoration effect of the miscellaneous electrochemical catalysis to carbon-to-nitrogen compound；The electricity that N doping is taken full advantage of in carbon-to-nitrogen compound is urged
Change the important function in activity；The stability for how improving catalyst fully considered.The present invention first by nickel, cobalt, iron from
Son formed ethylenediamine complex compound, and by them according to a certain percentage adulterate enter carbon-to-nitrogen composite structure in, while play this three
Electroactive humidification of the metal to catalyst is planted, and the mutual synergistic effect of these metals is utilized, to pole
The earth improves the electroactive of catalyst；Using gelatin and melamine as carbon source and nitrogen source, and due to melamine
Nitrogen content is very high, to which after substep is pyrolyzed, nitrogen is mixed in a manner of in situ in carbon structure, ensure that nitrogen high in product contains
Amount；Using the spontaneous polymerization of dopamine, one layer of carbon-to-nitrogen compound protective layer is formed in catalyst particle surface, to greatly carry
The high stability and electro catalytic activity of catalyst.
Specific implementation mode
Embodiment 1
（1）By the Ni (CH of 8.6 g3COO)2×4H2O, the Fe (CH of 0.9g3COO)2×4H2Co (the CH of O and 1.8g3COO)2×
4H2O is dissolved in water, is made into 500mL solution, and 7-70mL ethylenediamines are then slowly added into the aqueous solution, it is small to be stirred at room temperature 2
When；2.5 g gelatin are then added, acquired solution is heated to 50oC is simultaneously stirred 1 hour, until forming uniform mixture.
（2）25g melamines are added into said mixture, is sufficiently stirred 2 hours, so that melamine is fully dispersed in molten
In liquid, unit for uniform suspension is formed.Then, which is transferred in Rotary Evaporators, under vacuum, in 80oIt is evaporated under C, shape
At solid matter 40oIt is dried in vacuo 24 hours under C, obtains catalyst precursor -1.
（3）Above-mentioned catalyst precursor -1 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 300 oC keeps 2h at this temperature；Then, 800 are continuously heating to identical heating rate oC is kept at this temperature
2 h；Subsequent cooled to room temperature, obtains catalyst precursor -2.
（4）Isopropyl alcohol and water is pressed 1:2 volume ratios form mixed solvent, are then added three（Methylol）Aminomethane fills
Homogeneous solution is formed after dividing stirring, makes three（Methylol）The quality (g) of aminomethane and mixed solvent:Volume (mL)=1:1000；
Then 5g catalyst precursors -2 are added in the 2500mL homogeneous solutions, after gained mixture is ultrasonically treated 1 h, are added
1g dopamines continue that 48h is stirred at room temperature；Mixture is filtered later, is washed with water twice, obtained solid is 40oThe vacuum of C
It is 24 hours dry in drier, obtain catalyst precursor -3.
（5）Above-mentioned catalyst precursor -3 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 850 oC keeps 2h, subsequent cooled to room temperature to obtain catalyst at this temperature.
（6）By common three electrodes measurement method, with Ag/AgCl (sat. KCl) be reference electrode, platinized platinum be to electrode,
Respectively in acidity（0.5 mol L-1 H2SO4）, alkalinity（1 mol L-1NaOH）And neutrality（1 mol L-1 KNO3）In solution,
Test catalyst towards oxygen reduction reaction（ORR）Take-off potential and Limited diffusion current density（Electrode rotation rate 2000
rpm）, test catalyst is to oxygen evolution reaction（OER）Take-off potential.Test result is：
It is acid（0.5 mol L-1 H2SO4）：0.54 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities
5.4 mA cm-2, 1.35 V of OER deposition potentials (vs AgAgCl)；
Alkalinity（1 mol L-1NaOH）：- 0.05 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 4.1
mA cm-2, 0.45 V of OER deposition potentials (vs AgAgCl)；
It is neutral（1 mol L-1 KNO3）：0.2 V of ORR take-off potentials (vs AgAgCl), 4.8 mA of ORR Limited diffusion current densities
cm-2, 0.85 V of OER deposition potentials (vs AgAgCl).
Embodiment 2
（1）By the Ni (CH of 45 g3COO)2×4H2O, the Fe (CH of 5g3COO)2×4H2Co (the CH of O and 10g3COO)2×4H2O is molten
Yu Shui is made into 500mL solution, and 36mL ethylenediamines are then slowly added into the aqueous solution, is stirred at room temperature 2 hours；Then
25g gelatin is added, acquired solution is heated to 50oC is simultaneously stirred 1 hour, until forming uniform mixture.
（2）130g melamines are added into said mixture, is sufficiently stirred 2 hours, melamine is made to be fully dispersed in
In solution, unit for uniform suspension is formed.Then, which is transferred in Rotary Evaporators, under vacuum, in 80oIt is evaporated under C,
The solid matter of formation is 40oIt is dried in vacuo 24 hours under C, obtains catalyst precursor -1.
（3）Above-mentioned catalyst precursor -1 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 300 oC keeps 2 h at this temperature；Then, 800 are continuously heating to identical heating rate oC is protected at this temperature
Hold 2 h；Subsequent cooled to room temperature, obtains catalyst precursor -2.
（4）Isopropyl alcohol and water is pressed 1:2 volume ratios form mixed solvent, are then added three（Methylol）Aminomethane fills
Homogeneous solution is formed after dividing stirring, makes three（Methylol）The quality (g) of aminomethane and mixed solvent:Volume (mL)=1:1000；
Then 5g catalyst precursors -2 are added in the 2500mL homogeneous solutions, after gained mixture is ultrasonically treated 1 h, are added
25g dopamines continue that 48h is stirred at room temperature；Mixture is filtered later, is washed with water twice, obtained solid is 40oC's is true
It is 24 hours dry in empty drier, obtain catalyst precursor -3.
（5）Above-mentioned catalyst precursor -3 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 850 oC keeps 2h, subsequent cooled to room temperature to obtain catalyst at this temperature.
（6）Test method and step（1）It is identical.Test result is：
It is acid（0.5 mol L-1 H2SO4）：0.58 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities
6.5 mA cm-2, 1.30 V of OER deposition potentials (vs AgAgCl)；
Alkalinity（1 mol L-1NaOH）：- 0.01 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 6.1
mA cm-2, 0.40 V of OER deposition potentials (vs AgAgCl)；
It is neutral（1 mol L-1 KNO3）：0.25 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 5.8
mA cm-2, 0.82 V of OER deposition potentials (vs AgAgCl).
Embodiment 3
（1）By the Ni (CH of 86 g3COO)2×4H2O, the Fe (CH of 9g3COO)2×4H2Co (the CH of O and 18g3COO)2×4H2O is molten
Yu Shui is made into 500mL solution, and 70mL ethylenediamines are then slowly added into the aqueous solution, is stirred at room temperature 2 hours；Then
50g gelatin is added, acquired solution is heated to 50oC is simultaneously stirred 1 hour, until forming uniform mixture.
（2）250g melamines are added into said mixture, is sufficiently stirred 2 hours, melamine is made to be fully dispersed in
In solution, unit for uniform suspension is formed.Then, which is transferred in Rotary Evaporators, under vacuum, in 80oIt is evaporated under C,
The solid matter of formation is 40oIt is dried in vacuo 24 hours under C, obtains catalyst precursor -1.
（3）Above-mentioned catalyst precursor -1 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 300 oC keeps 2h at this temperature；Then, 800 are continuously heating to identical heating rate oC is kept at this temperature
2 h；Subsequent cooled to room temperature, obtains catalyst precursor -2.
（4）Isopropyl alcohol and water is pressed 1:2 volume ratios form mixed solvent, are then added three（Methylol）Aminomethane fills
Homogeneous solution is formed after dividing stirring, makes three（Methylol）The quality (g) of aminomethane and mixed solvent:Volume (mL)=1:1000；
Then 5g catalyst precursors -2 are added in the 2500mL homogeneous solutions, after gained mixture is ultrasonically treated 1 h, are added
50g dopamines continue that 48h is stirred at room temperature；Mixture is filtered later, is washed with water twice, obtained solid is 40oC's is true
It is 24 hours dry in empty drier, obtain catalyst precursor -3.
（5）Above-mentioned catalyst precursor -3 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 850 oC keeps 2h, subsequent cooled to room temperature to obtain catalyst at this temperature.
（6）Test method and step（1）It is identical.Test result is：
It is acid（0.5 mol L-1 H2SO4）：0.55 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities
6.4 mA cm-2, 1.31 V of OER deposition potentials (vs AgAgCl)；
Alkalinity（1 mol L-1NaOH）：- 0.04 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 5.9
mA cm-2, OER deposition potentials 0.44V (vs AgAgCl)；
It is neutral（1 mol L-1 KNO3）：0.22 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 5.8
mA cm-2, 0.84 V of OER deposition potentials (vs AgAgCl).
Embodiment 4
Step（1）And step（2）With embodiment（2）The step of（1）And step（2）It is identical.
（3）Above-mentioned catalyst precursor -1 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 400oC keeps 2h at this temperature；Then, 900 are continuously heating to identical heating rateoC is kept at this temperature
3h；Subsequent cooled to room temperature, obtains catalyst precursor -2.
Step（4）And step（5）With embodiment（2）The step of（4）And step（5）It is identical.
（6）Test method and step（1）It is identical.Test result is：
It is acid（0.5 mol L-1 H2SO4）：0.59 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities
6.6 mA cm-2, 1.31 V of OER deposition potentials (vs AgAgCl)；
Alkalinity（1 mol L-1NaOH）：- 0.03 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 6.2
mA cm-2, 0.44 V of OER deposition potentials (vs AgAgCl)；
It is neutral（1 mol L-1 KNO3）：0.24 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 5.9
mA cm-2, 0.83 V of OER deposition potentials (vs AgAgCl).
Embodiment 5
Step（1）And step（2）With embodiment（2）The step of（1）And step（2）It is identical.
（3）Above-mentioned catalyst precursor -1 is transferred in pipe reaction stove, nitrogen is passed through, with 5oC min-1Speed heating
To 500 oC keeps 5h at this temperature；Then, 1000 are continuously heating to identical heating rate oC is protected at this temperature
Hold 5h；Subsequent cooled to room temperature, obtains catalyst precursor -2.
Step（4）And step（5）With embodiment（2）The step of（4）And step（5）It is identical.
（6）Test method and step（1）It is identical.Test result is：
It is acid（0.5 mol L-1 H2SO4）：0.55 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities
5.8 mA cm-2, 1.36 V of OER deposition potentials (vs AgAgCl)；
Alkalinity（1 mol L-1NaOH）：- 0.10 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 5.5
mA cm-2, OER deposition potentials 0.48V (vs AgAgCl)；
It is neutral（1 mol L-1 KNO3）：0.26 V of ORR take-off potentials (vs AgAgCl), ORR Limited diffusion current densities 4.9
mA cm-2, OER deposition potentials 0.84V (vs AgAgCl).
Claims (2)
1. a kind of preparation method of nickel-cobalt-iron/carbon-to-nitrogen material of carbon-to-nitrogen compound cladding, characterized in that including following step
Suddenly：
（1）It prepares and contains ferrous acetate (Fe (CH3COO)2×4H2O), nickel acetate (Ni (CH3COO)2×4H2) and cobalt acetate O
(Co(CH3COO)2×4H2O the aqueous solution of salt-mixture) is then slowly added to ethylenediamine into the aqueous solution, stirs at room temperature
It mixes；Gelatin is then added, acquired solution is heated to 50oC is simultaneously stirred, until forming uniform mixture；
In the aqueous solution, nickel ion, ferrous ion and the total content of cobalt ions are 0.5 ~ 5 wt%；In the aqueous solution, nickel
The mass ratio of ion, ferrous ion and cobalt ions is 1:（0.1~0.2）：（0.2~0.8）；The addition of the ethylenediamine be nickel from
3 times of son, ferrous ion and cobalt ions gross mass；The addition of the gelatin is：The mass percent of gelatin in aqueous solution
For 0.5 ~ 10 %；
（2）Melamine is added into said mixture, is sufficiently stirred, melamine is made to be fully dispersed in solution, is formed equal
Even suspension；Then, by the suspension 80oIt is evaporated under C vacuum conditions, the solid matter of formation is 40oIt is dried in vacuo, obtains under C
Catalyst precursor -1；
The addition of the melamine is：The mass percent of melamine in the mixture is 5 ~ 50 %；
（3）Above-mentioned catalyst precursor -1 is transferred in reaction vessel, nitrogen is passed through, with 5oC min-1Speed be warming up to 300oC ~ 500 oC, certain time is kept at this temperature；Then, 800 are continuously heating to identical heating rate oC ~ 1000oC, certain time is kept at this temperature；Subsequent cooled to room temperature, obtains catalyst precursor -2；
（4）Isopropyl alcohol and water is pressed 1:2 volume ratios form mixed solvent, are then added three（Methylol）Aminomethane fully stirs
Homogeneous solution is formed after mixing, and makes three（Methylol）The quality (g) of aminomethane and mixed solvent:Volume (mL)=1:1000；Then
Above-mentioned catalyst precursor -2 is added in the homogeneous solution, after gained mixture is ultrasonically treated, adds dopamine, is continued
It is sufficiently stirred at room temperature；Mixture is filtered later, is washed, obtained solid is 40oThe vacuum drying of C, before obtaining catalyst
Drive body -3；
The quality (g) of the catalyst precursor -2 and homogeneous solution:Volume (mL)=1:500；Dopamine and complex catalyst precursor
The mass ratio of body -2 is（0.2 ~ 10）:1；
（5）Above-mentioned catalyst precursor -3 is transferred in reaction vessel, nitrogen is passed through, with 5oC min-1Speed be warming up to 850oC, keep at this temperature certain time, subsequent cooled to room temperature obtains catalyst.
2. a kind of nickel-cobalt-iron/carbon-to-nitrogen material of the carbon-to-nitrogen compound cladding prepared according to the method is to oxygen reduction reaction
（ORR）Electro catalytic activity and to oxygen evolution reaction（OER）Electro catalytic activity test in terms of application.
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| CN112133933A (en) * | 2020-09-20 | 2020-12-25 | 湖南科技大学 | Preparation method of iron-cobalt-platinum-loaded three-dimensional network surface hollow carbon sphere compound, product and application thereof |
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| CN113101962A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Porous carbon layer protection catalyst for activating persulfate, preparation method and application |
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| CN111203264A (en) * | 2020-03-19 | 2020-05-29 | 湘潭大学 | Novel iron-nickel-nitrogen co-doped carbon catalyst and preparation method and application thereof |
| CN111203264B (en) * | 2020-03-19 | 2022-08-16 | 湘潭大学 | Iron-nickel-nitrogen co-doped carbon catalyst and preparation method and application thereof |
| CN111842919A (en) * | 2020-07-31 | 2020-10-30 | 河北农业大学 | Preparation method of ultra-small nickel-iron nanocluster and ultra-small nickel-iron nanocluster |
| CN112133933A (en) * | 2020-09-20 | 2020-12-25 | 湖南科技大学 | Preparation method of iron-cobalt-platinum-loaded three-dimensional network surface hollow carbon sphere compound, product and application thereof |
| CN113078330A (en) * | 2021-04-09 | 2021-07-06 | 湖南科技大学 | Porous carbon-doped platinum-supported catalyst and preparation and application thereof |
| CN113078330B (en) * | 2021-04-09 | 2022-04-22 | 湖南科技大学 | Porous carbon-doped platinum-supported catalyst and preparation and application thereof |
| CN113101962A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Porous carbon layer protection catalyst for activating persulfate, preparation method and application |
| CN115228495A (en) * | 2022-06-17 | 2022-10-25 | 北京化工大学 | Calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater |
| CN115228495B (en) * | 2022-06-17 | 2023-12-15 | 北京化工大学 | Calcium-based carbon-coated ozone oxidation catalyst for advanced treatment of salt-containing organic wastewater |
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