CN110215930A - The carbon-coated Co base MOF derived material of N doping and preparation method and applications - Google Patents
The carbon-coated Co base MOF derived material of N doping and preparation method and applications Download PDFInfo
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- CN110215930A CN110215930A CN201910522874.6A CN201910522874A CN110215930A CN 110215930 A CN110215930 A CN 110215930A CN 201910522874 A CN201910522874 A CN 201910522874A CN 110215930 A CN110215930 A CN 110215930A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 152
- 239000000463 material Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 189
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 31
- 239000008247 solid mixture Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims description 63
- 238000005253 cladding Methods 0.000 claims description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 8
- 230000004224 protection Effects 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims 1
- 239000000467 phytic acid Substances 0.000 claims 1
- 229940068041 phytic acid Drugs 0.000 claims 1
- 235000002949 phytic acid Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 39
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- -1 cooling Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 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—
-
- B01J35/615—
-
- 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 preparation methods of the carbon-coated Co base MOF derived material of N doping, the following steps are included: preparation metal organic framework compound ZIF-67, cobalt nitrate and methylimidazole is taken to be dissolved in reaction kettle with water, reaction temperature is 150~200 DEG C, reaction time 2h obtains metal organic framework compound ZIF-67 after reaction is cooling；Solid mixture is prepared, takes metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine to be dissolved in the water to obtain mixed solution, mixed solution is freeze-dried, obtain solid mixture；The carbon-coated Co base MOF derived material of N doping is prepared, solid mixture is placed in stove, and is purged with argon gas, is 800~1000 DEG C of calcining 2h in temperature, cooling obtains the carbon-coated Co base MOF derived material of N doping.Raw material is conveniently easy to get in the preparation process, and synthetic route is simple, and obtained derived material all has preferable catalytic effect in the reaction of electrolysis water anodic and cathode reaction.
Description
Technical field
The present invention relates to the technical fields of catalyst, specifically, refer to that a kind of carbon-coated Co base MOF of N doping is derivative
Material and preparation method thereof and the derivative Co-CoP composite material and preparation method of nitrogen-doped carbon cladding MOF.
Background technique
Currently, traditional energy resource supply has been unable to meet the demand of people, the use of fossil energy will cause more serious
Environmental pollution, the forms of electricity generation of water power will cause the change of natural ecology, and nuclear energy power generation has potential radiation risk, underground heat
Power generation may result in the natural calamities such as earthquake, and therefore, safe and clean Hydrogen Energy becomes a kind of ideal renewable energy.
But Hydrogen Energy is a kind of secondary energy sources, it cannot can be directly from nature as non-renewable energy such as fossil energy or solar energy
It obtains, it must be produced by certain method using other energy.
In nature, hydrogen is easily and oxygen is combined into water, it is necessary to hydrogen be separated from the water out with the method for electrolysis.In reality
During the electrolysis water on border, the factors such as two electrode reactions can be dropped due to IR lead to the generation of overpotential, cause the big of energy
Amount is lost, and discovery can effectively reduce overpotential using electrolysis water catalyst in research.
Existing electrolysis water catalyst is mostly noble metal-based catalysts, but there are more to ask for noble metal-based catalysts
Topic, for example in electrolysis water catalytic process, the reserves of noble metal are limited, catalytic activity is poor, catalytic effect is poor, it is big not to be able to satisfy
The demand of scale commercial, using noble metal will cause at the same time, increased production cost.
Summary of the invention
The present invention provides a kind of carbon-coated Co base MOF derived material of N doping and preparation method thereof and nitrogen-doped carbon cladding
MOF derives Co-CoP composite material and preparation method, and exist in the prior art for solving: noble metal catalyst is in electrolysis water
In catalytic process, the reserves of noble metal are limited, and catalytic activity is poor, and catalytic effect is larger, and is not able to satisfy large-scale commercial applications
The technical issues of change demand.
The first purpose of this invention is to provide a kind of preparation side of carbon-coated Co base MOF derived material of N doping
Method, comprising the following steps:
Prepare metal organic framework compound ZIF-67
Cobalt nitrate and methylimidazole is taken to be dissolved in reaction kettle with water, reaction temperature is 150~200 DEG C, reaction time 2h,
Metal organic framework compound ZIF-67 is obtained after reaction is cooling；
Prepare solid mixture
It takes metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine to be dissolved in the water to be mixed
Mixed solution is freeze-dried by solution, obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 600~1000 DEG C of calcining 2h in temperature, it is cold
But the carbon-coated Co base MOF derived material of N doping is obtained.
In order to preferably realize the present invention, further, cobalt nitrate and methylimidazole is taken to be dissolved in reaction kettle with water, instead
Answering temperature is 180 DEG C, reaction time 2h, obtains metal organic framework compound ZIF-67 after reaction is cooling.
In order to preferably realize the present invention, further, solid mixture is placed in stove, and is blown with argon gas
It sweeps, is 800 DEG C of calcining 2h in temperature, cooling obtains Co base MOF derived material.
It illustrates herein, preferably argon gas, if selecting air as protective gas, will cause as protective gas
Carbon is reacted with the oxygen in air, generates CO2, it is unfavorable for the generation of reaction；It is to have in whole reaction process high temperature calcining
Machine carbon conversion is to have the inorganic carbon of electric conductivity, and furthermore 800 DEG C or more of calcination temperature improves the degree of graphitization of inorganic carbon,
Further enhance electric conductivity；Although high temperature is conducive to increase the electric conductivity of carbon, temperature is excessively high to make metal agglomeration, therefore
800 DEG C are the more excellent temperature chosen after overtesting.
In order to preferably realize the present invention, further, the time of the freeze-drying is 12~48h；Temperature is 0~10
℃。
It is preferred that common freeze-drying time is 12~48 hours, temperature is 0 to~10 DEG C, and usually the time is longer, temperature
More lower, better.After being freeze-dried in this way, the moisture inside material can be removed as far as possible, and maintain that material is original to be received
Rice structure.
Second object of the present invention is to provide a kind of carbon-coated Co base MOF derived material of N doping, by above-mentioned system
Preparation Method is made.
Third object of the present invention is that providing the carbon-coated Co base MOF derived material of N doping is catalyzed material in electrolysis water
Expect the application in direction.
Fourth object of the present invention is to provide a kind of nitrogen-doped carbon cladding MOF preparation of derivative Co-CoP composite material
Method is mixed according to the carbon-coated Co base MOF derived material of N doping obtained above with phosphorus source, is protected in 300~600 DEG C of argon gas
1~5h is calcined in shield, and the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.
It is preferred that calcining 2 hours in 500 DEG C of argon gas protections, being primarily due to, which is 500 DEG C, so that phosphide is sufficiently decomposed, and have
Conducive to the phosphorus reaction of compound and generation.But reaction time process may cause by-product generation, therefore be within 2 hours one excellent
Select the time.
In order to preferably realize the present invention, further, phosphorus source is selected from hypophosphites, hypophosphite, phosphoric acid, plant
Acid, hydrophosphate or red phosphorus, the hydrophosphate are selected from dihydric phosphate or hydrophosphate.It is during the reaction preferably phosphorus
It is safer to be primarily due to phosphorus source for source.
Of the invention the 5th is designed to provide a kind of derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF, by upper
Preparation method is stated to be made.
Of the invention the 6th is designed to provide the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF and urges in electrolysis water
Change the application in material direction.
Working principle:
The present invention provides a kind of preparation method of carbon-coated Co base MOF derived material of N doping, closes by using hydro-thermal
It is prepared at freeze-drying and high-temperature calcination work compound.Wherein MOF is metal-organic framework compound ZIF-67.
By long-term the study found that overpotential can be efficiently reduced using electrolysis water catalyst, and then the loss of energy is reduced, mentioned
High working efficiency.
Existing electrolysis water catalyst is mostly noble metal-based catalysts, and the metal-based catalyst using noble metal preparation exists
It is expensive, and reserves are limited, so that the effect of noble metal-based catalysts is bad, and are not able to satisfy the need of large-scale commercial
It asks.
The present invention is by being made metal organic framework compound ZIF-67 for cobalt nitrate and methylimidazole hydrothermal synthesis reaction
(referred to as: MOF), which is purple, using the derivatization of metal organic framework compound ZIF-67, by metal organic frame
Compound ZIF-67 and polyvinylpyrrolidone and melamine dissolve, and are then freeze-dried, obtain solid mixture, should
Solid mixture is purple, obtains the carbon-coated Co base MOF derived material of N doping by high-temperature calcination, by being freeze-dried,
Derived material is changed into solid gel, realizes metal organic framework compound particle in polyvinylpyrrolidone gel uniformly
Distribution, reduces the reunion of metal organic framework compound, realizes the purpose of stabilized scattering nano material.
The nanometer derived material of package base metal nano particle or metallic compound, low-priced gold are produced by above-mentioned method
Belong to or its compound has preferable electrolysis water at the nanoscale and urges performance.By long-term the study found that metal has machine frame
Frame compound ZIF-67 material easily causes material to reunite and accumulates, influence its catalytic activity since this is as the property of nano material,
Metal organic framework compound ZIF-67 material can be dispersed in by introducing polyvinylpyrrolidone and freeze-drying process poly-
In vinylpyrrolidone solid gel, the reunion of metal organic framework compound ZIF-67 material is avoided.And metal organic frame
Compound particle makes self-contained Co atom be limited in the carbon of metal organic framework compound in calcination process as template
In matter frame, reduce increase and the agglomeration of Co nano particle, and then improve the catalytic activity of derived material.
Specific works mechanism is that polyvinylpyrrolidone and metal organic framework compound ZIF-67 material are crosslinked, and is led to
Cross the mixed solution that metal organic framework compound ZIF-67 material is solved homogeneously in polyvinylpyrrolidone and melamine
In, it can be achieved that metal organic framework compound ZIF-67 material it is evenly dispersed, then by freeze-drying process, aqueous solution is used
Liquid nitrogen cools down rapidly, and metal organic framework compound ZIF-67 material is avoided to reunite or settle after solution left standstill, then will freezing
Derived material is placed in freeze drier dry afterwards, and can not change metal while excluding derived material itself moisture has machine frame
The microstructure of frame compound ZIF-67 material is limited in metal organic framework compound ZIF-67 material nanoparticle poly-
In the organic frame of vinylpyrrolidone, realizes its good dispersion and avoid reuniting.
But since metal organic framework compound ZIF-67 material itself does not have catalytic activity, also do not have conduction
Property, and the nitrogen-doped carbon and metallic nano-particle that obtain after being calcined by high temperature anaerobic have catalytic activity, therefore need metal
Organic frame compound ZIF-67 material carries out high temperature cabonization, obtains spreading out for conductive N doping carbonaceous substrate coating metal particles
Green material.Melamine is added during the reaction, the content of nitrogen-doped carbon in subsequent material can be improved, to obtain a large amount of
The highly conductive nitrogen-doped carbon with catalytic activity, and then enhance its catalytic activity.
In conclusion we are by by metal organic framework compound ZIF-67 material and melamine, polyvinyl pyrrole
Alkanone dissolves in aqueous solution, then carries out freeze-drying process, can get evenly dispersed metal organic framework compound ZIF-67
The polyvinylpyrrolidone solid gel of material inhibits the reunion accumulation of metal organic framework compound ZIF-67 material.Simultaneously
The introducing of melamine makes metal organic framework compound ZIF-67 material-melamine-polyvinylpyrrolidone solid gel
It can get the highly conductive nitrogen-doped carbon of a large amount of tool catalytic activity when calcining, the catalysis for improving material to a certain extent is living
Property.
In addition, derived material and the metal ion of organo-functional group complexing are changed into nano-metal particle after calcining, it is to spread out
The major catalytic site of green material.Meanwhile the Co atom of metal organic framework compound ZIF-67 material surface is catalyzed around it
Carbon spontaneously form carbon nanotube, be improved the specific surface area of material, increase its specific surface area, again further
Bright, the length of the carbon nanotube of generation is dozens to a few hundred nanometers.
The carbon-coated Co base MOF derived material of the N doping as made from above-mentioned preparation method, the derived material are being electrolysed
Water catalyst direction has efficient performance, and since raw material is easy to get and cheap, operating procedure is simple, therefore it is big to be more suitable for commercialization
Large-scale production.
The present invention also provides a kind of preparation methods of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF, and being will be above-mentioned
The carbon-coated Co base MOF derived material of N doping obtained is mixed with phosphate, calcines 2h under the protection of argon gas, cooling,
Composite material is obtained, by having the derivative Co-CoP composite material of finally obtained MOF within the scope of full PH
There is preferable catalytic effect, overcomes the shortcomings that metal-based catalyst can only be catalyzed under alkalinity and neutral environment.
Long-term the study found that pure metal can only be applied to the electrolysis water under alkalinity and neutral environment, this is to limit
Use scope is made, in order to improve use scope, researcher, which studies for a long period of time, to find to obtain in transition metal/carbon material composition
In nanocomposite, metal phosphide has broader pH application range relative to pure metal, further demonstrates gold
Belong to phosphide also can apply to acid condition on this basis.In addition, proving metal by DFT Density function theory structure
Phosphide is better than pure metal for the catalytic effect of electrolysis water.Therefore, nitrogen-doped carbon cladding MOF provided by the present invention is derivative
Co-CoP composite material has more efficient electrolysis water catalyst, which is better than other electrolysis water catalyst.
The beneficial effect of the embodiment of the present invention is:
The present invention is mixed to get by metal organic framework compound ZIF-67 with polyvinylpyrrolidone and melamine
Mixed solution, and be freeze-dried, solid mixture is calcined, the carbon-coated Co base MOF derived material of N doping is made, it should
Raw material is conveniently easy to get in preparation process, and synthetic route is simple, and obtained derived material electrolysis water anodic reaction and
Cathode reaction all has preferable catalytic effect；
The present invention passes through freeze-drying during preparing N doping carbon-coated Co base MOF derived material, realizes metal
Organic frame compound particle is uniformly distributed in polyvinylpyrrolidone gel, reduces the group of metal organic framework compound
It is poly-, realize the purpose of stabilized scattering nano material；
The present invention is by making self-contained Co atom calcined using metal organic framework compound particle as template
It is limited in journey in the carbonaceous frame of metal organic framework compound, reduces increase and the agglomeration of Co nano particle, into
And improve the catalytic activity of derived material；
The present invention is more advantageous to derived material ratio by the carbon nanotube that its surface increasingly generates in high-temperature burning process
The raising of surface area, the progress that can more promote catalysis to react；
The present invention coats nitrogen-doped carbon during preparing nitrogen-doped carbon cladding MOF derivative Co-CoP composite material
Co base MOF derived material mixed with phosphate, calcine, obtain composite material, by phosphatization, nano-metal particle be changed into
Nano metal phosphide particle has effectively widened the PH use scope of catalyst, most by the long-term further surface of research
The composite material obtained eventually all has preferable catalytic effect within the scope of full pH, improves the electrolysis water catalysis effect of composite material
Fruit further overcomes the shortcomings that metal-based catalyst can only be catalyzed under alkalinity and neutral environment.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is 1 solid mixture electron microscope picture of the embodiment of the present invention；
Fig. 2 is the carbon-coated Co base MOF derived material electron microscope picture of 1 N doping of the embodiment of the present invention；
Fig. 3 is the X-ray diffractogram of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention；
Fig. 4 is that the nitrogen adsorption-desorption of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention is tested
Figure；
Fig. 5 is the schematic diagram of internal structure of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention；
Fig. 6 is the evolving hydrogen reaction catalytic effect diagram of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention；
Fig. 7 is that the oxygen evolution reaction catalytic effect of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention is illustrated
Figure；
Fig. 8 is the impedance behavior schematic diagram of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention；
Fig. 9 is the equivalent simulation circuit figure of the carbon-coated Co base MOF derived material of 1 N doping of the embodiment of the present invention.
Figure 10 is 20000000 times of amplification that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF
Scanning Electron microscope figure (SEM figure)；
Figure 11 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats derivative 20000000 times of the amplification of Co-CoP composite material of MOF
Projection electron microscope figure (TEM figure)；
Figure 12 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The nitrogen adsorption-desorption figure (BET figure) of the Co base MOF derived material of cladding；
Figure 13 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The graph of pore diameter distribution of the Co base MOF derived material of cladding
Figure 14 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The X-ray diffractogram spectrogram of the Co base MOF derived material of cladding
Figure 15 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The evolving hydrogen reaction LSV of the Co base MOF derived material of cladding schemes
Figure 16 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The oxygen evolution reaction LSV of the Co base MOF derived material of cladding schemes
Figure 17 is that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF and 1 nitrogen-doped carbon of embodiment
The EIS AC impedance figure of the Co base MOF derived material of cladding.
Figure 18 is the equivalent simulation circuit figure that 2 nitrogen-doped carbon of the embodiment of the present invention coats the derivative Co-CoP composite material of MOF.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being usually described and illustrated herein in the accompanying drawings is implemented
The component of example can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1:
A kind of preparation method of the carbon-coated Co base MOF derived material of N doping
Prepare metal organic framework compound ZIF-67
0.4g cobalt nitrate and 3g methylimidazole is taken to be dissolved in autoclave with 20ml water, reaction temperature is 150~200
DEG C, reaction time 2h in high case baking oven obtains the metal organic framework compound ZIF-67 of purple after reaction is cooling；
Prepare solid mixture
1g metal organic framework compound ZIF-67,1g polyvinylpyrrolidone and 1g melamine is taken to be dissolved in 100ml
Mixed solution is obtained in water, mixed solution is freeze-dried, and obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 600~1000 DEG C of calcining 2h in temperature, it is cold
But the carbon-coated Co base MOF derived material of N doping is obtained.
Description of test:
Take above-mentioned presoma solid mixture (polyvinylpyrrolidone-melamine-metal organic framework compound ZIF-
67) solid mixture surface topography, is observed by JSM-7500F scanning electron microscope (SEM), as shown in Figure 1, can from figure
With find out the surface of entire composite material compared with out-of-flatness, it is more at fold, but entire material is complete entirety, is not occurred
The sign of any fracture.
The Co base MOF derived material of above-mentioned finally obtained product nitrogen-doped carbon cladding is scanned into electricity by JSM-7500F
The pattern of the electrolysis water catalysis material of sub- microscope (SEM) observation derived material, as shown in Figure 2.By SEM photograph it is found that metal
Organic frame compound ZIF-67 has preferable dispersion effect in carbon matrix, after calcination at high temperature, since metal has machine frame
Cobalt in frame compound ZIF-67 is reacted with carbon-based material, is occurred largely in metal organic framework compound ZIF-67 appearance
Nano tube structure.It is living with superior catalytic to disclose it for this special good dispersibility of composite construction and nano material
The reason of property.
Pass through X-ray diffraction (XRD): test is using DX 2700BH type X-ray diffractometer (the limited public affairs of the great first instrument in Dandong
Department) analysis 800 DEG C made from the carbon-coated Co base MOF derived material-electrolysis water catalyst of N doping, using Cu target, K α radiation
Source, 10 °/min of scanning speed, scanning range are 10 °~80 °, as shown in Figure 3.According to the characteristic peak of substance itself, composed from XRD
Figure show elctro-catalyst at being grouped as, predominantly carbon, cobalt, 44.8 °, 51.2 ° and 76.1 ° of diffraction maximum spreading out corresponding to Co
Peak is penetrated, 26.5 ° of corresponding diffraction maximums can belong to the diffraction maximum of C.
Test (BET) by nitrogen adsorption-desorption: test uses full-automatic BET specific surface (product) analysis tester (shellfish
Scientific and technological (Beijing) Co., Ltd of scholar's moral instrument) analysis, full aperture range test is carried out using nitrogen, as shown in Figure 4.BET figure is taken off
The specific surface area size for having shown material, in 800 DEG C of obtained carbon-coated Co base MOF derived material-catalyst Co-CNT/ of N doping
The specific surface area of NC is 238m2·g-1Left and right.
It is derivative by using the carbon-coated Co base MOF of 20 projection electron microscope of Tecnai G2 (TEM) observation N doping
The internal structure of the electrolysis water catalysis material of material, as shown in Figure 5.By TEM photo it is found that cobalt nano-particle has in carbon matrix
There is a preferable dispersion effect, partial size is about more than ten to tens nanometer.
It is tested by the linear voltammetric scan of evolving hydrogen reaction (HER-LSV): using CHI760E (the limited public affairs of Shanghai Chen Hua instrument
Department) catalytic effect of catalyst is tested, and three-electrode system is used, sample is the carbon-coated Co of N doping obtained at 800 DEG C
Base MOF derived material-catalyst, the potassium hydroxide aqueous solution for the 1mol/L that test environment is pH=14, as shown in Figure 6.By urging
The scanning linearity volt-ampere test LSV curve graph of agent is it is found that the evolving hydrogen reaction overpotential obtained under the sweep speed of 1mV/s is
237mV shows that there is material preferable electro-catalysis hydrogen catalytic effect is precipitated.
It is tested by the linear voltammetric scan of oxygen evolution reaction (OER-LSV): using CHI760E (the limited public affairs of Shanghai Chen Hua instrument
Department) catalytic effect of catalyst is tested, and three-electrode system is used, sample is the carbon-coated Co of N doping obtained at 800 DEG C
Base MOF derived material-catalyst, the potassium hydroxide aqueous solution for the 1mol/L that test environment is pH=14, as shown in Figure 7.By urging
The scanning linearity volt-ampere test LSV curve graph of agent is it is found that the oxygen evolution reaction overpotential obtained under the sweep speed of 1mV/s is
337mV shows that material has preferable electro-catalysis oxygen evolution catalytic effect.
Pass through AC impedence method (EIS) testing impedance to the carbon-coated Co base MOF derived material of N doping: using
The electrochemical impedance spectroscopy of CHI760E (Shanghai Chen Hua Instrument Ltd.) the test carbon-coated Co base MOF derived material of N doping
(EIS), frequency range 105~10-2Hz, signal is 10mV sine wave, and uses three-electrode system, and test environment is pH=14
1mol/L sodium hydrate aqueous solution, be made Nyquist figure, as shown in Figure 8.
In the impedance behavior of Study of Catalyst, the equivalent simulation circuit type of accurate judgement catalyst is very crucial.Make
Nyquist data are calculated and simulated with Zsimpwin software and different equivalent circuits, calculate and analog result can be anti-
The equivalent simulation circuit situation of catalyst should be gone out.This experiment removes analysis impedance modal data according to data and Zsimpwin software, can
Know the equivalent simulation circuit type of the carbon-coated Co base MOF derived material of N doping are as follows: R (QR), wherein R represents resistance, and Q is represented
Capacitor.As shown in Figure 9.
By above-mentioned experiment it can be concluded that the carbon-coated Co base MOF derived material of N doping provided by the present invention is in electricity
The reaction of solution water anodic and cathode reaction all have preferable catalytic effect.
Embodiment 2:
The carbon-coated Co base MOF derived material of N doping that embodiment 1 obtains is mixed with phosphorus source, is protected in 500 DEG C of argon gas
It is calcined 2 hours in shield, the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.
Description of test
Using the derivative Co-CoP composite material of JSM-7500F scanning electron microscope (SEM) observation nitrogen-doped carbon cladding MOF
Electrolysis water catalysis material pattern, as shown in Figure 10.By SEM photograph it is found that MOF is in carbon matrix has preferable dispersion effect
Fruit.After calcination at high temperature, since the cobalt in MOF is reacted with carbon-based material, there is a large amount of nanotube in composite material appearance
Structure, the length of nanotube are dozens to a few hundred nanometers.This special good dispersibility of composite construction and nano material,
Disclosing it has the reason of superior catalytic activity.
The derivative CoP of MOF using 20 projection electron microscope of Tecnai G2 (TEM) observation nitrogen-doped carbon matrix cladding is multiple
The internal structure of the electrolysis water catalysis material of condensation material, as shown in figure 11.By TEM photo it is found that CoP nano particle is in carbon matrix
In there is preferable dispersion effect, partial size is about more than ten to tens nanometer.
Nitrogen adsorption-desorption tests (BET): test uses full-automatic BET specific surface (product) analysis tester (Bei Shide
Instrument science and technology (Beijing) Co., Ltd) analysis, full aperture range test is carried out using nitrogen, test object is 1 gained of embodiment
Product: the carbon-coated Co base MOF derived material of N doping, 2 resulting product nitrogen-doped carbon of embodiment coat the derivative Co- of MOF
CoP composite material, test result are as shown in figure 12.BET figure discloses the specific surface area size of material, and nitrogen-doped carbon coats MOF
The specific surface area of derivative Co-CoP composite material is 250m2·g-1Left and right, the ratio of the carbon-coated Co base MOF derived material of N doping
Surface area is 238m2·g-1Left and right.
Pore-size distribution test: test is using full-automatic BET specific surface (product) analysis tester (Bei Shide instrument science and technology (north
Capital) Co., Ltd) analysis, full aperture range test is carried out using nitrogen, test object is 1 resulting product of embodiment: nitrogen is mixed
Miscellaneous carbon-coated Co base MOF derived material, 2 resulting product nitrogen-doped carbon of embodiment coat the derivative Co-CoP composite material of MOF,
Test result is as shown in figure 13.Pore-size distribution test discloses in the detection range of 0-100nm, and nitrogen-doped carbon cladding MOF spreads out
Raw Co-CoP composite material and the carbon-coated Co base MOF derived material of N doping all have micropore (0-2nm), mesoporous (2-50nm)
With three kinds of microscopic aperture structures of macropore (50nm or more), and three kinds of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
Aperture is all larger than the carbon-coated Co base MOF derived material of N doping.
X ray diffracting spectrum: test object is 1 resulting product of embodiment: the derivative material of the carbon-coated Co base MOF of N doping
Material, 2 resulting product nitrogen-doped carbon of embodiment coat the derivative Co-CoP composite material of MOF, as shown in figure 14.From map
Arrive, 36.4 ° of corresponding diffraction maximums are attributed to the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF, and 44.8 °, 51.2 ° and
76.1 ° diffraction maximum correspond to the diffraction maximum of Co, 26.5 ° of corresponding diffraction maximums can belong to the diffraction maximum of C.
Evolving hydrogen reaction: test object is 1 resulting product of embodiment: the carbon-coated Co base MOF derived material of N doping, real
Apply the derivative Co-CoP composite material of 2 resulting product nitrogen-doped carbon of example cladding MOF.As shown in Figure 15, nitrogen-doped carbon cladding MOF spreads out
The evolving hydrogen reaction take-off potential of raw Co-CoP composite material is 0.02V vs.RHE, and it is anti-liberation of hydrogen can to occur under extremely low overpotential
It answers, in 10mA/cm2Overpotential of hydrogen evolution under current density is 152mV, shows that the derivative Co-CoP of nitrogen-doped carbon cladding MOF is compound
Material has excellent catalytic activity of hydrogen evolution.And the evolving hydrogen reaction take-off potential of the carbon-coated Co base MOF derived material of N doping
For 0.71V vs.RHE, evolving hydrogen reaction can occur under extremely low overpotential, in 10mA/cm2Liberation of hydrogen under current density is excessively electric
Position is 237mV, shows that the carbon-coated Co base MOF derived material of N doping has good catalytic activity of hydrogen evolution.
Oxygen evolution reaction: test object is 1 resulting product of embodiment: the carbon-coated Co base MOF derived material of N doping, real
Apply the derivative Co-CoP composite material of 2 resulting product nitrogen-doped carbon of example cladding MOF.As shown in figure 16, nitrogen-doped carbon cladding MOF spreads out
The oxygen evolution reaction take-off potential of raw Co-CoP composite material is 1.304V vs.RHE, can occur to analyse oxygen under extremely low overpotential
Reaction, in 10mA/cm2Overpotential for oxygen evolution under current density is 295mV, shows that the derivative Co-CoP of nitrogen-doped carbon cladding MOF is multiple
Condensation material has excellent analysis oxygen catalytic performance.And the oxygen evolution reaction of the carbon-coated Co base MOF derived material of N doping originates electricity
Position is 1.452V vs.RHE, oxygen evolution reaction can occur under extremely low overpotential, in 10mA/cm2Analysis oxygen mistake under current density
Current potential is 337mV, shows that the carbon-coated Co base MOF derived material of N doping has good analysis oxygen catalytic performance.
EIS ac impedance measurement: test object is 1 resulting product of embodiment: the carbon-coated Co base MOF of N doping is derivative
Material, 2 resulting product nitrogen-doped carbon of embodiment coat the derivative Co-CoP composite material of MOF.As shown in Figure 17, nitrogen-doped carbon packet
The derivative Co-CoP composite material of MOF is covered with the carbon-coated Co base MOF derived material of N doping to all have lesser impedance (real part connects
Nearly 10,50) imaginary part is no more than, and the impedance of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is coated less than nitrogen-doped carbon
Co base MOF derived material, illustrate that the electric conductivity of catalysis material is preferable.
In the impedance behavior of Study of Catalyst, the equivalent simulation circuit type of accurate judgement catalyst is very crucial.Make
Nyquist data are calculated and simulated with Zsimpwin software and different equivalent circuits, calculate and analog result can be anti-
The equivalent simulation circuit situation of catalyst should be gone out.This experiment removes analysis impedance modal data according to data and Zsimpwin software, can
Know the equivalent simulation circuit type of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF are as follows: R (QR), wherein R represents resistance, Q
Represent capacitor.As shown in figure 18.
Embodiment 3:
A kind of preparation method of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
Prepare metal organic framework compound ZIF-67
Cobalt nitrate and methylimidazole is taken to be dissolved in autoclave with water, reaction temperature is 150~200 DEG C, and high case is dried
Reaction time 2h in case obtains the metal organic framework compound ZIF-67 of purple after reaction is cooling；
Prepare solid mixture
It takes metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine to be dissolved in 100ml water to obtain
To mixed solution, mixed solution is freeze-dried, obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 600 DEG C of calcining 2h in temperature, cooling obtains
The carbon-coated Co base MOF derived material of N doping
Prepare the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
The carbon-coated Co base MOF derived material of N doping is mixed with phosphorus source, is calcined 3 hours in 300 DEG C of argon gas protections,
The derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.The composite material is used for catalytic electrolysis water.
Test result shows that the specific surface area of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF of preparation is
212.5m2·g-1, evolving hydrogen reaction take-off potential is 0.46V vs.RHE, in 10mA/cm2Overpotential of hydrogen evolution under current density
For 192mV, oxygen evolution reaction take-off potential is 1.361V vs.RHE, and oxygen evolution reaction can occur under extremely low overpotential,
10mA/cm2Overpotential for oxygen evolution under current density is 352mV, shows that the derivative Co-CoP of nitrogen-doped carbon cladding MOF of preparation is compound
Material has the excellent aqueous energy of catalytic electrolysis.
Embodiment 4:
A kind of preparation method of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
Prepare metal organic framework compound ZIF-67
Cobalt nitrate and methylimidazole is taken to be dissolved in autoclave with water, reaction temperature is 150~200 DEG C, and high case is dried
Reaction time 2h in case obtains the metal organic framework compound ZIF-67 of purple after reaction is cooling；
Prepare solid mixture
It takes metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine to be dissolved in 100ml water to obtain
To mixed solution, mixed solution is freeze-dried, obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 800 DEG C of calcining 4h in temperature, cooling obtains
The carbon-coated Co base MOF derived material of N doping
Prepare the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
The carbon-coated Co base MOF derived material of N doping is mixed with phosphorus source, is calcined 2 hours in 400 DEG C of argon gas protections,
The derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.The composite material is used for catalytic electrolysis water.
Test result shows that the specific surface area for preparing the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is
237.4m2·g-1, evolving hydrogen reaction take-off potential is 0.32V vs.RHE, in 10mA/cm2Overpotential of hydrogen evolution under current density
For 163mV, oxygen evolution reaction take-off potential is 1.323V vs.RHE, and oxygen evolution reaction can occur under extremely low overpotential,
10mA/cm2Overpotential for oxygen evolution under current density is 325mV, shows that the derivative Co-CoP of nitrogen-doped carbon cladding MOF of preparation is compound
Material has the excellent aqueous energy of catalytic electrolysis.
Embodiment 5:
A kind of preparation method of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
Prepare metal organic framework compound ZIF-67
Cobalt nitrate and methylimidazole is taken to be dissolved in autoclave with water, reaction temperature is 150~200 DEG C, and high case is dried
Reaction time 2h in case obtains the metal organic framework compound ZIF-67 of purple after reaction is cooling；
Prepare solid mixture
It takes metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine to be dissolved in 100ml water to obtain
To mixed solution, mixed solution is freeze-dried, obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 900 DEG C of calcining 3h in temperature, cooling obtains
The carbon-coated Co base MOF derived material of N doping
Prepare the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF
The carbon-coated Co base MOF derived material of N doping is mixed with phosphorus source, is calcined 3 hours in 450 DEG C of argon gas protections,
The derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.The composite material is used for catalytic electrolysis water.
Test result shows that the specific surface area of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF of preparation is
242.5m2·g-1, evolving hydrogen reaction take-off potential is 0.24V vs.RHE, in 10mA/cm2Overpotential of hydrogen evolution under current density
For 157mV, oxygen evolution reaction take-off potential is 1.311V vs.RHE, and oxygen evolution reaction can occur under extremely low overpotential,
10mA/cm2Overpotential for oxygen evolution under current density is 307mV, shows that the derivative Co-CoP of nitrogen-doped carbon cladding MOF of preparation is compound
Material has the excellent aqueous energy of catalytic electrolysis.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that are as follows:
A variety of change, modification, replacement and modification, the present invention can be carried out to these embodiments by not departing under the principle of the present invention and objective
Range be defined by the claims and their equivalents.
Claims (10)
1. a kind of preparation method of the carbon-coated Co base MOF derived material of N doping, it is characterised in that: the following steps are included:
Prepare metal organic framework compound ZIF-67
Cobalt nitrate and methylimidazole is taken to be dissolved in reaction kettle with water, reaction temperature is 150~200 DEG C, reaction time 2h, reaction
Metal organic framework compound ZIF-67 is obtained after cooling；
Prepare solid mixture
Take metal organic framework compound ZIF-67, polyvinylpyrrolidone and melamine be dissolved in the water to obtain mix it is molten
Mixed solution is freeze-dried by liquid, obtains solid mixture；
Prepare the carbon-coated Co base MOF derived material of N doping
Solid mixture is placed in stove, and is purged with argon gas, is 600~1000 DEG C of 1~5h of calcining in temperature, it is cooling
Obtain the carbon-coated Co base MOF derived material of N doping.
2. preparation method according to claim 1, it is characterised in that: cobalt nitrate and methylimidazole is taken to be dissolved in reaction with water
In kettle, reaction temperature is 180 DEG C, reaction time 2h, obtains metal organic framework compound ZIF-67 after reaction is cooling.
3. preparation method according to claim 1, it is characterised in that: solid mixture is placed in stove, and uses argon gas
It is purged, is 800 DEG C of calcining 2h in temperature, cooling obtains the carbon-coated Co base MOF derived material of N doping.
4. preparation method according to claim 1, it is characterised in that: the time of the freeze-drying is 12~48h；Temperature
It is 0~10 DEG C.
5. a kind of as the derivative material of the carbon-coated Co base MOF of N doping is made in the described in any item preparation methods of Claims 1 to 4
Material.
6. a kind of carbon-coated Co base MOF derived material of N doping a kind of as claimed in claim 5 is in electrolysis water catalysis material
The application in direction.
7. a kind of preparation method of the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF, it is characterised in that: a kind of as right is wanted
The carbon-coated Co base MOF derived material of N doping made from asking 5 is mixed with phosphorus source, calcines 1 in 300~600 DEG C of argon gas protections
~5 hours, the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is obtained after natural cooling.
8. preparation method according to claim 7, it is characterised in that: phosphorus source be selected from hypophosphites, hypophosphite,
Phosphoric acid, phytic acid, hydrophosphate or red phosphorus, the hydrophosphate are selected from dihydric phosphate or hydrophosphate.
9. the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF is made in preparation method according to claim 7 or 8.
10. the derivative Co-CoP composite material of nitrogen-doped carbon cladding MOF according to claim 9 is in electrolysis water catalysis material side
To application.
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