CN110331414A - A kind of copper-based nano stick array foam copper-base composite electrode material and its preparation method and application that MOF is compound - Google Patents
A kind of copper-based nano stick array foam copper-base composite electrode material and its preparation method and application that MOF is compound Download PDFInfo
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- CN110331414A CN110331414A CN201910267713.7A CN201910267713A CN110331414A CN 110331414 A CN110331414 A CN 110331414A CN 201910267713 A CN201910267713 A CN 201910267713A CN 110331414 A CN110331414 A CN 110331414A
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- copper
- mof
- foam copper
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- stick array
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- 239000010949 copper Substances 0.000 title claims abstract description 131
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 114
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000006260 foam Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 16
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 16
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 34
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000005750 Copper hydroxide Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000002073 nanorod Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000002604 ultrasonography Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000549556 Nanos Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 therefore Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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- 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
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Abstract
The invention discloses a kind of copper-based nano stick array foam copper-base composite electrode materials and its preparation method and application that MOF is compound.The MOF compound copper-based nano stick array foam copper-base composite electrode material is characterized in that, using foam copper as substrate, the surface growth of the foam copper Kocide SD nanometer stick array compound with MOF；The MOF is ZIF-67.Preparation method grows Cu (OH) using in-situ synthesis directly in foam copper substrate2Nanometer stick array, then with Cu (OH)2Nanometer stick array is that substrate passes through template oriented growth in its surface growth MOF particle, and the electrode material with electrocatalysis characteristic is obtained finally by dehydration.The composite material under alkaline condition stablize by performance, and recycling degree with higher, biggish electrochemical surface area greatly improves the catalytic activity of material；Preparation method preparation process is simple, sintering temperature is low, low energy consumption in preparation process, is convenient for industrialized production.
Description
Technical field
The present invention relates to a kind of copper-based nano stick array foam copper-base composite electrode material that MOF is compound and its preparation sides
Method and purposes belong to electrolysis water catalysis analysis oxygen technical field.
Background technique
The energy is the most important motive force of human productivity development as the various movable foundation stones of production of human society.
From ancient times to the present, the energy that fossil energy is mainly utilized as the mankind, depletion rate become to be getting faster with the development of the mankind,
Since especially into industrialization society, existing storage will be depleted within several centuries.The consumption of fossil energy
Problem of environmental pollution is brought, therefore, developing sustainable clean alternative energy source is the task of top priority.Due to combustion of hydrogen process energy
It discharges huge energy and product is water, therefore, hydrogen is considered a kind of sustainable clean energy resource.Come from environmental-friendly angle
It says, electrochemical catalysis hydrogen production by water decomposition is to prepare one of desirable route of hydrogen.Electrolysis water includes the production oxygen reaction (OER) of anode
With the evolving hydrogen reaction (HER) of cathode, wherein OER reaction is the slow process of dynamics of four electronics transfers, generally requires to disappear
Consume higher energy.Currently, noble metal-based catalysts (RuO2/IrO2) it is a kind of efficient production VPO catalysts, however these your gold
Belong to the expensive of base catalyst, reserves are limited, limit its heavy industrialization application.Therefore, it can be held to meet development
The oxygen-separating catalyst of the requirement of the continuous energy, development and application high efficiency low cost seems very heavy to substitute expensive noble metal catalyst
It wants.
In recent years, have some base metals and be used as oxygen-separating catalyst, but catalytic stability and catalytic performance
Industrialization production requirements can not be reached.Therefore, develop a kind of cheap, easily prepared and high performance non-precious metal catalyst pair
Promote oxygen evolution reaction industrialization development important in inhibiting.Research finds that the oxygen evolution reaction under alkaline condition has pollution-free, behaviour
Make convenience, technology maturation, be easy to the advantages that large-scale production, becomes one of research hotspot.But oxygen evolution reaction under alkaline condition
Catalyst it is poor there are catalytic activity and stability the problems such as, it is also necessary to further research.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a kind of copper-based nanos that MOF is compound
Stick array foam copper-base composite electrode material (ZIF-67 Cu (OH)2@foam copper) and its preparation method and application.It is described compound
Electrode material catalytic activity with higher, stronger stability, higher analysis oxygen performance and recycling degree.Its preparation process
Simply, sintering temperature is low, and low energy consumption in preparation process, is convenient for industrialized production.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of copper-based nano stick array foam copper-base composite electrode material (ZIF-67 Cu (OH) that MOF is compound2@foam
Copper), which is characterized in that for the combination electrode material using foam copper as substrate, the surface growth of the foam copper has MOF compound
Kocide SD nanometer stick array；The MOF is ZIF-67.
The present invention also provides the preparation sides of above-mentioned MOF compound copper-based nano stick array foam copper-base composite electrode material
Method, which comprises the following steps:
1) ammonium persulfate aqueous solution and potassium hydroxide aqueous solution are configured to precursor solution, by foam copper immerse it is described before
It drives in liquid solution and is reacted, after reaction, wash drying, obtaining surface growth has metallic copper hydroxide nanorod array
Foam copper (Cu (OH)2@foam copper)；
2) foam copper that the growth of surface obtained by step 1) has Kocide SD nanometer stick array is put into the presoma of ZIF-67
In solution, reaction a period of time loads ZIF-67 particle in the nanorod surfaces by crystallization, aging, and washing and drying obtains
MOF without dehydration compound copper-based nano stick array foam copper-base composite electrode material；
3) the copper-based nano stick array foam copper-base composite electrode material that the MOF without dehydration obtained by step 2) is compound
It is made annealing treatment, obtains the compound copper-based nano stick array foam copper-base composite electrode material (ZIF-67 of final product MOF
Cu(OH)2@foam copper).
According to the above scheme, it is preferable that the molar ratio of ammonium persulfate described in step 1) and the potassium hydroxide is 0.5~4:
20~50.It is highly preferred that the molar ratio of the ammonium persulfate and the potassium hydroxide is 1:25.
According to the above scheme, it is preferable that the concentration of ammonium persulfate aqueous solution described in step 1) is 0.1-1mol/L；The hydrogen
The concentration for aoxidizing aqueous solutions of potassium is 6-15mol/L.
According to the above scheme, it is preferable that pretreatment of the foam copper described in step 1) through past surface and oil contaminant and oxide layer, tool
Body are as follows: defoamed copper surface and oil contaminant and oxide layer using organic solvent and acid soak.
According to the above scheme, it is preferable that the temperature of reaction described in step 1) is room temperature, reaction time 10-60min.
According to the above scheme, it is preferable that in step 2), the precursor solution of the ZIF-67 is prepared to obtain by following methods:
Cobalt salt and methylimidazole are dissolved in methanol respectively, A, B solution is configured to, then AB solution is mixed, obtains
The precursor solution of the ZIF-67.It is highly preferred that the molar ratio of the cobalt salt and methylimidazole is 1~2:4~8.It is more excellent
Selection of land, the concentration range of solute is 0.01~0.1mol/L in the solution A, and the concentration range of solute is in the B solution
0.1~0.4mol/L.It is highly preferred that the cobalt salt is one or more of cobalt nitrate, cobalt chloride, cobaltous sulfate.
According to the above scheme, it is preferable that in step 2), the reaction specifically: then first stirring at normal temperature 1-10min stops
Stirring, be protected from light standing reaction 10~for 24 hours.
According to the above scheme, it is preferable that in step 3), the specific steps of the annealing are as follows: it is passed through under the conditions of Ar gas, with
The rate of 5 DEG C/min is warming up to 280-320 DEG C, after keeping the temperature 1~3h, is cooled to room temperature with the rate of 5 DEG C/min.
The present invention also provides the purposes of above-mentioned MOF compound copper-based nano stick array foam copper-base composite electrode material,
It is characterized in that, the combination electrode material can be used as the electrode or catalyst that are electrolysed elutriation oxygen.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
(1) electrolysis elutriation Oxygen Electrode Material of the present invention uses the novel inorganic of metallic copper hydroxide nanorod array
Functional material and metal organic frame carry out the composite material that compound method generates, and can effectively improve the stability of catalyst,
Further after annealing, it can be obviously improved its catalysis analysis oxygen performance under alkaline condition, make up existing Non-precious Metal Catalysts
The defect of agent.
(2) MOF of the present invention compound copper-based nano stick array foam copper-base composite electrode material, direct in-situ
It is grown on foam copper skeleton structure surface, as from carried catalyst, is made without any supplementary means directly as electrode
With.
(3) the preparation-obtained MOF of the present invention compound copper-based nano stick array foam copper-base composite electrode material has
The big advantage of surface area, provides more active sites, so its catalysis analysis oxygen better performances.
(4) stability of combination electrode material of the present invention is good, and recycling degree is high, can be widely used as electrolyzed alkaline water
Oxygen Electrode Material is analysed, is had broad application prospects.
(5) preparation process of combination electrode material of the present invention is simple, and sintering temperature is low, and low energy consumption in preparation process,
It is convenient for industrialized production.
Detailed description of the invention
Fig. 1 is that intermediate product prepared by 1 step b of the embodiment of the present invention is the metallic copper hydroxide grown on foam copper
The SEM of the array of object schemes.
Fig. 2 is that intermediate product prepared by 1 step c of the embodiment of the present invention is the compound copper-based nano of the MOF without dehydration
The SEM of stick array foam copper-base composite electrode schemes.
Fig. 3 is that the compound copper-based nano stick array foam of final product MOF prepared by 1 step d of the embodiment of the present invention is copper-based
The SEM of combination electrode material schemes.
Fig. 4 is ZIF-67@Cu (OH) prepared by Application Example 1 of the present invention2@foam copper is as working electrode in alkalinity
Under the conditions of analysis oxygen Experiment Polarization curve graph.Wherein curve 1 is ZIF-67@Cu (OH)2@foam copper, curve 2 are RuO2@foam
Copper.
Specific embodiment
Embodiment 1
A kind of preparation for the copper-based nano stick array foam copper-base composite electrode material that MOF is compound, comprising the following steps:
A, the pretreatment of foam copper: taking foam copper, is cut into 1cm × 2cm size, is placed in a beaker, and is added anhydrous
Ethyl alcohol pours out dehydrated alcohol after ultrasonic 15min to submerging, and the dilute hydrochloric acid of 1mol/L is added to submerging, water cleans after ultrasonic 15min
It is spare.
B, firstly, preparing precursor solution: measuring 30mL deionized water and be placed in a beaker, ammonium persulfate is then added
1.64g (7.2mmol) stirs ultrasound 15min, until stand-by after being completely dissolved；It measures 30mL deionized water to be placed in a beaker, so
Potassium hydroxide 10.1g (180mmol) is added afterwards, stirs ultrasound 15min, until ammonium persulfate solution is added after being completely dissolved, stirs
It is uniform to obtain the precursor solution.Then, it is added in Xiang Suoshu precursor solution through step a treated foam copper, room temperature is anti-
20min is answered, surface growth is obtained after separation, washing, drying Cu (OH)2Foam copper (the Cu (OH) of nanometer rods2@foam
Copper).
C, it measures 25mL methanol to be placed in a beaker, 0.29g (1mmol) cobalt nitrate is added, ultrasound is stand-by to being completely dissolved；Amount
It takes 25mL methanol to be placed in a beaker, 0.33g (4mmol) methylimidazole is added, cobalt nitrate is added to after being completely dissolved for ultrasound
Methanol solution is subsequently added into the Cu (OH) that step b is obtained2@foam copper is protected from light standing reaction after stirring at normal temperature 5min for 24 hours, reaction
It separates, wash afterwards, being drying to obtain the compound copper-based nano stick array foam copper-base composite electrode material of the MOF without dehydration
(ZIF-67@Cu(OH)2@foam copper).
D, the compound copper-based nano stick array@foam copper of the MOF prepared by step c without dehydration is put into tube furnace
In, it is passed through after argon gas 15min and is warming up to 300 DEG C with the rate of 5 DEG C/min, keep the temperature and room is cooled to the rate of 5 DEG C/min after 3h
Temperature obtains dewatered ZIF-67@Cu (OH)2@foam carbon/carbon-copper composite material.
Fig. 1 is the SEM figure of the array of the metallic copper hydroxide grown on foam copper prepared by the present embodiment step b,
Fig. 2 is the compound copper-based nano stick array foam copper-base composite electrode of the MOF without dehydration prepared by the present embodiment step c
SEM figure, Fig. 3 is the compound copper-based nano stick array@foam copper base composite electric of final product MOF prepared by embodiment step d
The SEM of pole material schemes.From can be seen that lamellar structure array is obvious in composite material in Fig. 1, Fig. 2, with 3D structure, from Fig. 3
In it can be seen that composite material after dehydration, still keeps good club shaped structure array, it is good that this illustrates that this material has
Thermal stability and porosity.
Embodiment 2
A kind of preparation for the copper-based nano stick array foam copper-base composite electrode material that MOF is compound, comprising the following steps:
A, the pretreatment of foam copper: taking foam copper, is cut into 1cm × 2cm size, is placed in a beaker, and is added anhydrous
Ethyl alcohol pours out dehydrated alcohol after ultrasonic 15min to submerging, and the dilute hydrochloric acid of 1mol/L is added to submerging, water cleans after ultrasonic 20min
It is spare.
B, firstly, preparing precursor solution: measuring 30mL deionized water and be placed in a beaker, ammonium persulfate is then added
1.64g (7.2mmol) stirs ultrasound 15min, until stand-by after being completely dissolved；It measures 30mL deionized water to be placed in a beaker, so
Potassium hydroxide 20.2g (360mmol) is added afterwards, stirs ultrasound 15min, until ammonium persulfate solution is added after being completely dissolved, stirs
It is uniform to obtain the precursor solution.Then, it is added in Xiang Suoshu precursor solution through step a treated foam copper, room temperature is anti-
10min is answered, obtaining growth after separation, washing, drying has Cu (OH)2Foam copper (the Cu (OH) of nanometer rods2@foam copper).
C, it measures 25mL methanol to be placed in a beaker, 0.29g (1mmol) cobalt nitrate is added, ultrasound is stand-by to being completely dissolved；Amount
It takes 25mL methanol to be placed in a beaker, 0.66g (8mmol) methylimidazole is added, cobalt nitrate is added to after being completely dissolved for ultrasound
Methanol solution is subsequently added into the Cu (OH) that step b is obtained2@foam copper is protected from light standing reaction 20h, reaction after stirring at normal temperature 5min
It separates, wash afterwards, being drying to obtain the compound copper-based nano stick array foam copper-base composite electrode material of the MOF without dehydration
(ZIF-67@Cu(OH)2@foam copper).
D, the compound copper-based nano stick array@foam copper of the MOF prepared by step c without dehydration is put into tube furnace
In, it is passed through after argon gas 15min and is warming up to 300 DEG C with the rate of 5 DEG C/min, keep the temperature and room is cooled to the rate of 5 DEG C/min after 2h
Temperature obtains dewatered ZIF-67@Cu (OH)2@foam carbon/carbon-copper composite material.
Embodiment 3
A kind of preparation for the copper-based nano stick array foam copper-base composite electrode material that MOF is compound, comprising the following steps:
A, the pretreatment of foam copper: taking foam copper, is cut into 1cm × 2cm size, is placed in a beaker, and is added anhydrous
Ethyl alcohol pours out dehydrated alcohol after ultrasonic 15min to submerging, and the dilute hydrochloric acid of 1mol/L is added to submerging, water cleans after ultrasonic 20min
It is spare.
B, firstly, preparing precursor solution: measuring 30mL deionized water and be placed in a beaker, ammonium persulfate is then added
1.64g (7.2mmol) stirs ultrasound 15min, until stand-by after being completely dissolved；It measures 30mL deionized water to be placed in a beaker, so
Potassium hydroxide 20.2g (360mmol) is added afterwards, stirs ultrasound 15min, until ammonium persulfate solution is added after being completely dissolved, stirs
It is uniform to obtain the precursor solution.Then, it is added in Xiang Suoshu precursor solution through step a treated foam copper, room temperature is anti-
20min is answered, obtaining growth after separation, washing, drying has Cu (OH)2Foam copper (the Cu (OH) of nanometer rods2@foam copper).
C, it measures 25mL methanol to be placed in a beaker, 0.29g (1mmol) cobalt nitrate is added, ultrasound is stand-by to being completely dissolved；Amount
It takes 25mL methanol to be placed in a beaker, 0.33g (4mmol) methylimidazole is added, cobalt nitrate is added to after being completely dissolved for ultrasound
Methanol solution is subsequently added into the Cu (OH) that step b is obtained2@foam copper is protected from light standing reaction 12h, reaction after stirring at normal temperature 5min
It separates, wash afterwards, being drying to obtain the compound copper-based nano stick array foam copper-base composite electrode material of the MOF without dehydration
(ZIF-67@Cu(OH)2@foam copper).
D, the compound copper-based nano stick array@foam copper of the MOF prepared by step c without dehydration is put into tube furnace
In, it is passed through after argon gas 15min and is warming up to 300 DEG C with the rate of 5 DEG C/min, keep the temperature and room is cooled to the rate of 5 DEG C/min after 3h
Temperature obtains dewatered ZIF-67@Cu (OH)2@foam carbon/carbon-copper composite material.
Embodiment 4
A kind of preparation for the copper-based nano stick array foam copper-base composite electrode material that MOF is compound, comprising the following steps:
A, the pretreatment of foam copper: taking foam copper, is cut into 1cm × 2cm size, is placed in a beaker, and is added anhydrous
Ethyl alcohol pours out dehydrated alcohol after ultrasonic 15min to submerging, and the dilute hydrochloric acid of 1mol/L is added to submerging, water cleans after ultrasonic 15min
It is spare.
B, firstly, preparing precursor solution: measuring 30mL deionized water and be placed in a beaker, ammonium persulfate is then added
1.64g (7.2mmol) stirs ultrasound 15min, until stand-by after being completely dissolved；It measures 30mL deionized water to be placed in a beaker, so
Potassium hydroxide 10.1g (180mmol) is added afterwards, stirs ultrasound 15min, until ammonium persulfate solution is added after being completely dissolved, stirs
It is uniform to obtain the precursor solution.Then, it is added in Xiang Suoshu precursor solution through step a treated foam copper, room temperature is anti-
20min is answered, obtaining growth after separation, washing, drying has Cu (OH)2Foam copper (the Cu (OH) of nanometer rods2@foam copper).
C, it measures 25mL methanol to be placed in a beaker, 0.29g (1mmol) cobalt nitrate is added, ultrasound is stand-by to being completely dissolved；Amount
It takes 25mL methanol to be placed in a beaker, 0.33g (4mmol) methylimidazole is added, cobalt nitrate is added to after being completely dissolved for ultrasound
Methanol solution is subsequently added into the Cu (OH) that step b is obtained2@foam copper is protected from light standing reaction 10h, reaction after stirring at normal temperature 5min
It separates, wash afterwards, being drying to obtain the compound copper-based nano stick array foam copper-base composite electrode material of the MOF without dehydration
(ZIF-67@Cu(OH)2@foam copper).
D, the compound copper-based nano stick array@foam copper of the MOF prepared by step c without dehydration is put into tube furnace
In, it is passed through after argon gas 15min and is warming up to 300 DEG C with the rate of 5 DEG C/min, keep the temperature and room is cooled to the rate of 5 DEG C/min after 1h
Temperature obtains dewatered ZIF-67@Cu (OH)2@foam carbon/carbon-copper composite material.
Application Example 1
The final product ZIF-67@Cu (OH) that will be prepared in embodiment 12@foam carbon/carbon-copper composite material is filled as electrolysis water
Anodic oxygen evolution reaction electrode (alternatively referred to as catalyst) is set, Electrochemical oxygen evolution experiment is carried out to it.Specific step is as follows:
Controlling test temperature is 25 DEG C；By the ZIF-67@Cu (OH) of 0.5cm × 0.5cm size2@foam copper
Composite material is used as to electrode assembling as reference electrode, graphite electrode at three directly as working electrode, saturated calomel electrode
Electrode system is respectively put into threeway electrolytic cell；The potassium hydroxide solution of 1mol/L is prepared, threeway electrolytic cell is added；Using following
Ring voltammetry is activated electrode, and curved scanning speed is 50mV/s, and scanning circle number is 30 circles；Polarization curve is tested,
Curved scanning speed is 2mV/s, and 85% IR compensation is carried out before testing.
Test and interpretation of result:
Using business RuO2@foam copper is tested as a control group, wherein business RuO2(ruthenic oxide) purchase in Shanghai Ah
Latin biochemical technology limited liability company, content 99.9%, RuO2@foam copper is prepared by drop coating drying means, specific to walk
Suddenly are as follows: by 4mg business RuO2Be dissolved in ultrasonic disperse 1h in 1mL alcohol dispersion liquid, after take 500 μ L dispersant liquid drops be added in 0.5cm ×
It on the foam copper of 0.5cm, is used after natural drying, RuO2Load capacity be 4mgcm-2。
The Electrochemical oxygen evolution experiment of catalyst prepared by Application Example 1, business RuO2The Electrochemical oxygen evolution of@foam copper
Experiment Polarization curve is as shown in Figure 4.Compare two curves, it can be seen that catalyst prepared by Application Example 1 of the present invention exists
Reach 10mA/cm in analysis oxygen experiment3Current density required for overpotential be 250mV, far below commercial foam nickel 324mV's
Overpotential shows good analysis oxygen catalytic performance, and illustrating the catalyst industrially has stronger application potential.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (12)
1. a kind of copper-based nano stick array foam copper-base composite electrode material that MOF is compound, which is characterized in that the compound electric
Pole material is using foam copper as substrate；The Kocide SD nanometer stick array that the surface growth of the foam copper has MOF compound；It is described
MOF is ZIF-67.
2. a kind of preparation method for the copper-based nano stick array foam copper-base composite electrode material that MOF is compound, which is characterized in that
The following steps are included:
1) ammonium persulfate aqueous solution and potassium hydroxide aqueous solution are configured to precursor solution, foam copper is immersed into the presoma
It is reacted in solution, after reaction, washs drying, obtain the bubble that surface growth has metallic copper hydroxide nanorod array
Foam copper；
2) foam copper that the growth of surface obtained by step 1) has Kocide SD nanometer stick array is put into the precursor solution of ZIF-67
In, reaction a period of time, washing and drying obtains the compound copper-based nano stick array@foam copper base composite electric of the MOF without dehydration
Pole material；
3) MOF without dehydration obtained by step 2) compound copper-based nano stick array foam copper-base composite electrode material is carried out
Annealing, obtains the compound copper-based nano stick array foam copper-base composite electrode material of final product MOF.
3. the preparation side of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the molar ratio of ammonium persulfate described in step 1) and the potassium hydroxide is 0.5~4:20~50.
4. the preparation side of MOF according to claim 3 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the molar ratio of ammonium persulfate described in step 1) and the potassium hydroxide is 1:25.
5. the preparation side of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the concentration of ammonium persulfate aqueous solution described in step 1) is 0.1-1mol/L；The potassium hydroxide aqueous solution
Concentration be 6-15mol/L.
6. the preparation side of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the temperature of reaction described in step 1) is room temperature, time 10-60min.
7. the preparation side of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that in step 2), the precursor solution of the ZIF-67 is prepared to obtain by following methods:
Cobalt salt and methylimidazole are dissolved in methanol respectively, are configured to A, B solution, then AB solution is mixed, is obtained described
The precursor solution of ZIF-67.
8. the preparation side of MOF according to claim 7 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the molar ratio of the cobalt salt and the methylimidazole is 1~2:4~8；The cobalt salt is cobalt nitrate, chlorine
Change one or more of cobalt, cobaltous sulfate.
9. the preparation side of MOF according to claim 7 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that the concentration range of solute is 0.01~0.1mol/L in the solution A, the concentration of solute in the B solution
Range is 0.1~0.4mol/L.
10. the preparation of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that in step 2), the reaction specifically: then first stirring at normal temperature 1-10min stops stirring, is protected from light quiet
Set reaction 10~for 24 hours.
11. the preparation of MOF according to claim 2 compound copper-based nano stick array foam copper-base composite electrode material
Method, which is characterized in that in step 3), the specific steps of the annealing are as follows: be passed through under the conditions of Ar gas, with 5 DEG C/min's
Rate is warming up to 280-320 DEG C, after keeping the temperature 1~3h, is cooled to room temperature with the rate of 5 DEG C/min.
12. the purposes of MOF described in claim 1 compound copper-based nano stick array foam copper-base composite electrode material, special
Sign is that the combination electrode material can be used as the electrode or catalyst that are electrolysed elutriation oxygen.
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