CN110124704A - A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate - Google Patents
A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate Download PDFInfo
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- CN110124704A CN110124704A CN201910530894.8A CN201910530894A CN110124704A CN 110124704 A CN110124704 A CN 110124704A CN 201910530894 A CN201910530894 A CN 201910530894A CN 110124704 A CN110124704 A CN 110124704A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 239000004744 fabric Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 125000005341 metaphosphate group Chemical group 0.000 title claims abstract description 16
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 229910052573 porcelain Inorganic materials 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 39
- 239000003054 catalyst Substances 0.000 abstract description 31
- 229910002441 CoNi Inorganic materials 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 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
- 238000012546 transfer Methods 0.000 description 6
- 229910018916 CoOOH Inorganic materials 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 229910002640 NiOOH Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- AHTSCRNWVSEMPI-UHFFFAOYSA-N gold;methane Chemical compound C.[Au] AHTSCRNWVSEMPI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 global warming Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001890 transfection Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- B01J35/61—
-
- 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
A kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate, the present invention relates to the preparation method fields of bimetallic metaphosphate modification carbon nano-composite material.The invention solves existing anode catalyst stability and catalytic activity are low, and noble metal and its oxide technical problem at high cost.This method: first by coprecipitation by Co bimetallic MOFs homoepitaxial on conductive carbon cloth, obtain CoNi (n)-ZIF nano-array, Low Temperature Solid-Phase phosphorylation reaction then carried out to it, obtains Co2‑xNixP4O12C nano array catalyst.Catalyst of the present invention is non-precious metal catalyst, reduces reaction cost, is precipitated with good catalytic activity to oxygen.Material prepared by the present invention is in electrolysis water oxygen evolution reaction.
Description
Technical field
The present invention relates to the preparation method fields of bimetallic metaphosphate modification carbon nano-composite material.
Background technique
Today's society, the development of the mankind and the energy are closely bound up.Past more than two in century, the energy resource supply of the mankind
Depend on the non-renewable fossil fuel such as petroleum, natural gas.But it is increasingly depleted with the consumption-types energy such as petroleum, coal
And many environmental problems caused by burning mineral fuel, such as global warming, air and water pollution, find a kind of green
Recyclable new energy is extremely urgent.In numerous energy, Hydrogen Energy is shown one's talent, it has, and combustion heat value is high, burns without dirt
The advantages that dye, abundant raw material, storage convenient transportation, be the clean energy resource of great competitiveness.In various hydrogen production process, electrolysis water
With its abundant raw material, the recyclability that hydrogen is produced and utilized becomes current optimal hydrogen production process for hydrogen manufacturing.However, oxygen evolution reaction
(OER,4OH-→H2O+O2+4e-) due to proton couple electronic transfer process step it is more, kinetic reaction is slow, serious to limit
The efficiency of entire energy conversion apparatus.Nowadays, the most common OER anode catalyst is noble metal and its oxide, still
Its stability is poor, at high cost, reserves are low seriously limits its large-scale application in electrolysis water oxygen evolution reaction.
Summary of the invention
The invention solves existing anode catalyst stability and catalytic activity are low, and noble metal and its oxide cost
High technical problem, and a kind of Co being supported in carbon cloth substrate is provided2-xNixP4O12The preparation method of C nano array.
A kind of Co being supported in carbon cloth substrate2-xNixP4O12The preparation method of C nano array, sequentially includes the following steps:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, then in dense HNO3Middle supersound washing, then
It is washed with water, dries, the carbon cloth that obtains that treated；
Two, by Co (NO3)2·6H2O and Ni (NO3)2·6H2O is distributed in deionized water, and magnetic agitation is uniform, is labeled as
Solution A；In deionized water by 2-methylimidazole dispersion, solution B is fallen under continuing magnetic force stirring action labeled as solution B
Enter in solution A, stir, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, continuously stir 2 at room temperature~
Then 6h takes out carbon cloth, cleaned repeatedly with deionized water, and then vacuum constant temperature is dry, obtains being supported on double gold on carbon cloth
Belong to MOF presoma；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, by the porcelain boat
It is placed at tube furnace downstream, another is equipped with NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, under an argon atmosphere
300~450 DEG C are warming up to, keeps the temperature 2~4h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 30~60min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co2-xNixP4O12CC nanometers of-C@multiple
Condensation material completes preparation；Wherein 0.11 ﹤ x ﹤ 2.
Wherein, it is 1 × 2cm that step 3, which immerses the size of carbon cloth in solution C,2, obtain being supported on carbon cloth in step 3
Bimetallic MOF presoma is CoNi (n)-ZIF@CC, and step 5 cleaning function is to remove excessive P powder.
The beneficial effects of the present invention are:
The present invention is using dimensional Co bimetallic organic frame (ZIF-67) as presoma and sacrifices template, by room temperature
Coprecipitation is constructed on carbon cloth, and 2D CoNi (n)-ZIF@CC nano-array is obtained, and then passes through later period Low Temperature Solid-Phase phosphorus
Acidization can be obtained by the carbon nano-array composite catalyst of the excellent bimetallic metaphosphate modification of catalytic performance.
The Co that the present invention obtains2-xNixP4O12- C@CC nanocomposite, the big specific surface area of two-dimensional nano piece can expose
More active sites points, ultra-thin thickness provide relatively comfortable charge transfer path, the array structure energy being made of nanometer sheet
The quick release for dramatically increasing contact of the material with electrolyte, being conducive to generate gas.By with conductive substrates composite lifting material
The electric conductivity and the more active sites of exposure of material, can greatly facilitate the transfer of electronics, in addition, matrix and active material
Collaboration coupling between material can also bring the promotion of activity and stability, and then enhance the electro catalytic activity of original material.Pass through
Metallic nickel ions adulterate the electronic structure that can optimize material, adjust the adsorption energy of intermediate, and then optimize the performance of material.Cause
This, is used as oxygen evolution reaction (OER), shows excellent catalytic activity, is 10mA/cm in current density2When, overpotential is only
230mV, slope 51.1mV/dec are lower than business noble metal catalyst IrO2@CC (overpotential 310mV), this explanation
Co1.6Ni0.4P4O12- C@CC is 10mA/cm in current density2When left and right, oxygen evolution reaction is rapider, i.e., is catalyzed compared to others
Agent, Co1.6Ni0.4P4O12- C@CC has faster oxygen evolution reaction dynamics in catalytic electrolysis elutriation oxygen reaction process, therefore urges
Change good activity.In addition, the catalyst by 1000 times CV recycle, current density decline seldom, by it is long under constant voltage when
Between 12h stability test, electric current is also held nearly constant, and shows excellent catalytic stability.
This material is shown for being electrolysed elutriation oxygen better than business IrO as non-precious metal catalyst2Electro-catalysis it is living
Property, reaction cost is reduced, this is preparation low cost, high catalytic activity, and the good new catalyst of stability is used for renewable energy
Source conversion provides new approaches.
The present invention is used to prepare Co2-xNixP4O12The material of-C CC nanocomposite, preparation is anti-for being electrolysed elutriation oxygen
Ying Zhong.
Detailed description of the invention
Fig. 1 is the XRD spectra of CoNi (n)-ZIF presoma of different proportion prepared by embodiment and comparative experiments；
Fig. 2 is Co prepared by embodiment and comparative experiments2-xNixP4O12The XRD spectra of-C@CC nanocomposite；
Fig. 3 is Co prepared by embodiment and comparative experiments2-xNixP4O12The Raman spectrogram of-C@CC nanocomposite；
Fig. 4 is Co prepared by embodiment and comparative experiments2-xNixP4O12The local Raman of-C@CC nanocomposite is composed
Figure；
Fig. 5 is scanning electron microscope (SEM) figure of treated the carbon cloth of embodiment one；
Fig. 6 is high power scanning electron microscope (SEM) figure of CoNi (1:0)-ZIF nano-array of comparative experiments preparation,
Fig. 7 is low power scanning electron microscope (SEM) figure of CoNi (1:0)-ZIF nano-array of comparative experiments preparation,
Fig. 8 is high power scanning electron microscope (SEM) figure of CoNi (8:1)-ZIF nano-array prepared by embodiment two,
Fig. 9 is low power scanning electron microscope (SEM) figure of CoNi (8:1)-ZIF nano-array prepared by embodiment two,
Figure 10 is high power scanning electron microscope (SEM) figure of CoNi (4:1)-ZIF nano-array prepared by embodiment one,
Figure 11 is low power scanning electron microscope (SEM) figure of CoNi (4:1)-ZIF nano-array prepared by embodiment one,
Figure 12 is high power scanning electron microscope (SEM) figure of CoNi (2:1)-ZIF nano-array prepared by embodiment three,
Figure 13 is low power scanning electron microscope (SEM) figure of CoNi (2:1)-ZIF nano-array prepared by embodiment three
Figure 14 is the Co of comparative experiments preparation2P4O12High power scanning electron microscope (SEM) figure of-C@CC nano-array,
Figure 15 is the Co of comparative experiments preparation2P4O12Low power scanning electron microscope (SEM) figure of-C@CC nano-array,
Figure 16 is Co prepared by embodiment two1.78Ni0.22P4O12The high power scanning electron microscope of-C@CC nano-array
(SEM) figure,
Figure 17 is Co prepared by embodiment two1.78Ni0.22P4O12The low power scanning electron microscope of-C@CC nano-array
(SEM) figure,
Figure 18 is Co prepared by embodiment one1.6Ni0.4P4O12The high power scanning electron microscope of-C@CC nano-array
(SEM) figure,
Figure 19 is Co prepared by embodiment one1.6Ni0.4P4O12The low power scanning electron microscope of-C@CC nano-array
(SEM) figure,
Figure 20 is Co prepared by embodiment three1.33Ni0.67P4O12The high power scanning electron microscope of-C@CC nano-array
(SEM) figure,
Figure 21 is Co prepared by embodiment three1.33Ni0.67P4O12The low power scanning electron microscope of-C@CC nano-array
(SEM) figure；
Figure 22 is Co prepared by embodiment one1.6Ni0.4P4O12The EDS of-C@CC nanocomposite schemes；
Figure 23 is Co prepared by embodiment one1.6Ni0.4P4O12The transmission electron microscope of-C@CC nanocomposite
(TEM) figure；
Figure 24 is Co prepared by embodiment one1.6Ni0.4P4O12The HRTEM of-C@CC nanocomposite schemes；
Figure 25 is Co prepared by embodiment one1.6Ni0.4P4O12The SAED of-C@CC nanocomposite schemes；
Co prepared by Figure 26 embodiment one1.6Ni0.4P4O12The angle of elevation annular dark-of-C CC nanocomposite is swept
Retouch the distribution diagram of element of transmitted electron image；
Figure 27 is the Co of embodiment preparation2-xNixP4O12Co prepared by-C@CC nanocomposite, comparative experiments2P4O12-C
Nanocomposite and blank carbon cloth, business IrO2Linear scan (LSV) curve graph of@CC；Wherein " 1 " represents
Co1.6Ni0.4P4O12- C, " 2 " represent Co1.78Ni0.22P4O12- C, " 3 " represent Co1.33Ni0.67P4O12- C, " 4 " represent Co2P4O12-
C, " 5 " represent IrO2@CC, " 6 " represent CC；
Figure 28 is the Co of embodiment preparation2-xNixP4O12Co prepared by-C@CC nanocomposite, comparative experiments2P4O12-C
Nanocomposite and business IrO2The Tafel slope figure of@CC；Wherein " 1 " represents Co1.6Ni0.4P4O12- C, " 2 " represent
Co1.78Ni0.22P4O12- C, " 3 " represent Co1.33Ni0.67P4O12- C, " 4 " represent Co2P4O12- C, " 5 " represent IrO2@CC；
Figure 29 is the Co of embodiment preparation2-xNixP4O12Co prepared by-C@CC nanocomposite, comparative experiments2P4O12-C
The effective active area-graph of nanocomposite；Wherein " 1 " represents Co1.6Ni0.4P4O12- C, " 2 " represent Co1.78Ni0.22P4O12-
C, " 3 " represent Co1.33Ni0.67P4O12- C, " 4 " represent Co2P4O12-C；
Figure 30 is the Co of embodiment preparation2-xNixP4O12Co prepared by-C@CC nanocomposite, comparative experiments2P4O12-C
The AC impedance figure of nanocomposite；Wherein " 1 " represents Co1.6Ni0.4P4O12- C, " 2 " represent Co1.78Ni0.22P4O12- C, " 3 "
Represent Co1.33Ni0.67P4O12- C, " 4 " represent Co2P4O12-C；
Figure 31 is Co prepared by embodiment one1.6Ni0.4P4O12The multistep current course figure of-C@CC nanocomposite；
Figure 32 is Co prepared by embodiment one1.6Ni0.4P4O12- C@CC nanocomposite carries out electricity in alkaline electrolyte
The polarization curve of the catalytic decomposition circle of elutriation oxygen reaction cycle 1000 front and back compares figure, wherein " ■ " represents 1 circle of circulation, "●" is represented
1000 circle of circulation；
Figure 33 is Co prepared by embodiment one1.6Ni0.4P4O12Electric current is at any time under constant voltage for-C@CC nanocomposite
Change curve；
Figure 34 is the Co recycled after 1000 circle CV1.6Ni0.4P4O12The SEM of-C@CC nanocomposite schemes (1 μm)；
Figure 35 is the Co recycled after 1000 circle CV1.6Ni0.4P4O12The TEM of-C@CC nanocomposite schemes (200nm)；
Figure 36 is the Co recycled after 1000 circle CV1.6Ni0.4P4O12The HRTEM of-C@CC nanocomposite schemes；
Figure 37 is the Co recycled before and after 1000 circle CV1.6Ni0.4P4O12- C@CC nanocomposite combination can be 772~
The Co element swarming of 810eV compares figure；
Figure 38 is the Co recycled before and after 1000 circle CV1.6Ni0.4P4O12- C@CC nanocomposite combination can be 128~
The P element swarming of 142eV compares figure；
Figure 39 is the Co recycled before and after 1000 circle CV1.6Ni0.4P4O12- C@CC nanocomposite combination can be 525~
The O element swarming of 540eV compares figure；
Figure 40 is the Co recycled before and after 1000 circle CV1.6Ni0.4P4O12The Raman spectrogram of-C@CC nanocomposite.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Specific embodiment 1: a kind of Co being supported in carbon cloth substrate of present embodiment2-xNixP4O12C nano array
Preparation method, sequentially include the following steps:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, then in dense HNO3Middle supersound washing, then
It is washed with water, dries, the carbon cloth that obtains that treated；
Two, by Co (NO3)2·6H2O and Ni (NO3)2·6H2O is distributed in deionized water, and magnetic agitation is uniform, is labeled as
Solution A；In deionized water by 2-methylimidazole dispersion, solution B is fallen under continuing magnetic force stirring action labeled as solution B
Enter in solution A, stir, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, continuously stir 2 at room temperature~
Then 6h takes out carbon cloth, cleaned repeatedly with deionized water, and then vacuum constant temperature is dry, obtains being supported on double gold on carbon cloth
Belong to MOF presoma；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, by the porcelain boat
It is placed at tube furnace downstream, another is equipped with NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, under an argon atmosphere
300~450 DEG C are warming up to, keeps the temperature 2~4h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 30~60min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co2-xNixP4O12CC nanometers of-C@multiple
Condensation material completes preparation；Wherein 0.11 ﹤ x ﹤ 2.
The Co that present embodiment obtains2-xNixP4O12- C@CC nanocomposite, the big specific surface area energy of two-dimensional nano piece
The more active sites points of exposure, ultra-thin thickness provide relatively comfortable charge transfer path, the array junctions being made of nanometer sheet
The quick release that structure can dramatically increase contact of the material with electrolyte, be conducive to generate gas.By with conductive substrates are compound mentions
The electric conductivity and the more active sites of exposure for rising material, can greatly facilitate the transfer of electronics, in addition, matrix and work
Property material between collaboration coupling can also bring activity and stability promotion, and then enhance original material electro catalytic activity.
The electronic structure that material can be optimized by metallic nickel ions doping adjusts the adsorption energy of intermediate, and then optimizes the property of material
Energy.Therefore, it is used as oxygen evolution reaction (OER), shows excellent catalytic activity, is 10mA/cm in current density2When, overpotential
Only 230mV is tested by long-time stability under constant voltage, and electric current is held nearly constant, and is shown excellent catalysis and is stablized
Property.
This material is shown for being electrolysed elutriation oxygen better than business IrO as non-precious metal catalyst2Electro-catalysis it is living
Property, reaction cost is reduced, this is preparation low cost, high catalytic activity, and the good new catalyst of stability is used for renewable energy
Source conversion provides new approaches.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: in dense HNO in step 13In
4~4.5h of supersound washing.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: Co in step 2 solution A
(NO3)2·6H2The concentration of O is 25~50mmol/L.It is other the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: step 2 solution A
Middle Ni (NO3)2·6H2The concentration of O is 2.9~25mmol/L.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: step 2 solution B
The concentration of middle 2-methylimidazole is 0.1~0.4mol/L.It is other identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: step 2 solution A
Volume ratio with solution B is 1: 1.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: true in step 3
Empty freeze-day with constant temperature temperature is 60~62 DEG C, drying time > 10h.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: in step 4
NaH2PO2·H2The quality of O is 1~2g.It is other identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: being controlled in step 4
Heating rate processed is 2~5 DEG C/min.It is other identical as one of specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: will in step 6
Step 5 repeats 4~5 times.It is other identical as one of specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of Co being supported in carbon cloth substrate of the present embodiment2-xNixP4O12The preparation method of C nano array, by following
Step carries out:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, 30min is washed respectively, then in dense HNO3
Middle supersound washing 4h, is washed with water and washs 30min, dries controlled at 60 DEG C, the carbon cloth that obtains that treated；
Two, by 0.4656g Co (NO3)2·6H2O and 0.1163g Ni (NO3)2·6H2O is distributed to 40mL deionized water
In, magnetic agitation is uniform, is labeled as solution A；1.3136g 2-methylimidazole is dispersed in 40mL deionized water, labeled as molten
Liquid B pours into solution B in solution A under continuing magnetic force stirring action, stirs 2min, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, and continuously stirs 4h at room temperature,
Then carbon cloth is taken out, is cleaned repeatedly with deionized water, then vacuum constant temperature is dry, and drying temperature is 60 DEG C, drying time >
10h obtains being supported on the bimetallic MOF presoma (CoNi (4:1)-ZIF@CC) on carbon cloth；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, by the porcelain boat
It is placed at tube furnace downstream, another is equipped with 1.5g NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, in argon gas
It is warming up to 400 DEG C under atmosphere, keeps the temperature 2h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 40min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co1.6Ni0.4P4O12CC nanometers of-C@
Composite material completes preparation.
Wherein, it is 1 × 2cm that step 3, which immerses the size of carbon cloth in solution C,2。
Embodiment two:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, 30min is washed respectively, then in dense HNO3
Middle supersound washing 4h, is washed with water and washs 30min, dries controlled at 60 DEG C, the carbon cloth that obtains that treated；
Two, by 0.5174g Co (NO3)2·6H2O and 0.0646g Ni (NO3)2·6H2O is distributed to 40mL deionized water
In, magnetic agitation is uniform, is labeled as solution A；1.3136g 2-methylimidazole is dispersed in 40mL deionized water, labeled as molten
Liquid B pours into solution B in solution A under continuing magnetic force stirring action, stirs 2min, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, and continuously stirs 4h at room temperature,
Then carbon cloth is taken out, is cleaned repeatedly with deionized water, then vacuum constant temperature is dry, and drying temperature is 60 DEG C, drying time >
10h obtains being supported on the bimetallic MOF presoma (CoNi (8:1)-ZIF@CC) on carbon cloth；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, by the porcelain boat
It is placed at tube furnace downstream, another is equipped with 1.5g NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, in argon gas
It is warming up to 400 DEG C under atmosphere, keeps the temperature 2h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 40min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co1.78Ni0.22P4O12CC nanometers of-C@
Composite material completes preparation.
Wherein, it is 1 × 2cm that step 3, which immerses the size of carbon cloth in solution C,2。
Embodiment three:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, 30min is washed respectively, then in dense HNO3
Middle supersound washing 4h, is washed with water and washs 30min, dries controlled at 60 DEG C, the carbon cloth that obtains that treated；
Two, by 0.3880g Co (NO3)2·6H2O and 0.1939g Ni (NO3)2·6H2O is distributed to 40mL deionized water
In, magnetic agitation is uniform, is labeled as solution A；1.3136g 2-methylimidazole is dispersed in 40mL deionized water, labeled as molten
Liquid B pours into solution B in solution A under continuing magnetic force stirring action, stirs 2min, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, and continuously stirs 4h at room temperature,
Then carbon cloth is taken out, is cleaned repeatedly with deionized water, then vacuum constant temperature is dry, and drying temperature is 60 DEG C, drying time >
10h obtains being supported on the bimetallic MOF presoma (CoNi (2:1)-ZIF@CC) on carbon cloth；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, by the porcelain boat
It is placed at tube furnace downstream, another is equipped with 1.5g NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, in argon gas
It is warming up to 400 DEG C under atmosphere, keeps the temperature 2h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 40min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co1.33Ni0.67P4O12CC nanometers of-C@
Composite material completes preparation.
Wherein, it is 1 × 2cm that step 3, which immerses the size of carbon cloth in solution C,2。
Comparative experiments:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, 30min is washed respectively, then in dense HNO3
Middle supersound washing 4h, is washed with water and washs 30min, dries controlled at 60 DEG C, the carbon cloth that obtains that treated；
Two, by 0.6525g Co (NO3)2·6H2O is distributed in 40mL deionized water, and magnetic agitation is uniform, labeled as molten
Liquid A；1.3136g 2-methylimidazole is dispersed in 40mL deionized water, solution B is labeled as, in continuing magnetic force stirring action
Under, solution B is poured into solution A, 2min is stirred, obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, and continuously stirs 4h at room temperature,
Then carbon cloth is taken out, is cleaned repeatedly with deionized water, then vacuum constant temperature is dry, and drying temperature is 60 DEG C, drying time >
10h obtains being supported on the Co-MOF presoma (ZIF-67@CC) on carbon cloth；
Four, the Co-MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, which is put
At tube furnace downstream, another is equipped with 1.5g NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, in argon gas gas
It is warming up to 400 DEG C under atmosphere, keeps the temperature 2h, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 40min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co2P4O12The nano combined material of-C@CC
Material completes preparation.
Wherein, it is 1 × 2cm that step 3, which immerses the size of carbon cloth in solution C,2。
The Co that embodiment one obtains1.6Ni0.4P4O12- C@CC nanocomposite catalyst is applied to electrocatalytic decomposition elutriation
It is 10mA/cm in current density in oxygen reaction2When, overpotential is only 230mV.
CoNi (4:1)-ZIF nano-array prepared by embodiment one ,-ZIF nanometers of battle arrays of CoNi (8:1) prepared by embodiment two
CoNi (1:0)-ZIF nano-array of CoNi (2:1)-ZIF nano-array and comparative experiments preparation prepared by column, embodiment three
For XRD spectra as shown in Figure 1, as can be seen from Fig., ZIF-67 presoma has 2D layer structure and a no any impurity, but with
The increase of Ni content, the XRD spectra of bimetallic CoNi (n)-ZIF of formation integrally fit like a glove, illustrate with ZIF-67
Ni is adulterated in ZIF-67 will not cause the change of structure, this is primarily due to Ni2+And Co2+With similar ionic radius,
It can occur mutually to replace in reaction process.
Co prepared by embodiment one1.6Ni0.4P4O12- C@CC nano-array, Co prepared by embodiment two1.78Ni0.22P4O12-
Co prepared by C@CC nano-array, embodiment three1.33Ni0.67P4O12The Co of C nano array and comparative experiments preparation2P4O12-C@
The XRD spectra of CC nano-array is as shown in Fig. 2, as can be seen from Fig., in addition to the peak of carbon cloth substrate, other peaks and monoclinic form
Co2P4O12And CoNiP4O12It matches, corresponding PDF card 86-2162 and 76-2283, to the peak at 2 θ=17.5-18.7 °
It amplifies, it can be seen from the figure that the peak position at (- 113) crystal face has slight offset as the content of doping Ni increases,
Caused by locally replacing lattice dilation caused by Co this is mainly due to Ni, which further illustrates us and successfully draws Ni
Enter in ZIF-67, and we successfully convert Co for CoNi (4:1)-ZIF presoma by Low Temperature Solid-Phase Phosphorylation events2- xNixP4O12C nano composite material.
Co prepared by embodiment one1.6Ni0.4P4O12- C@CC nano-array, Co prepared by embodiment two1.78Ni0.22P4O12-
Co prepared by C@CC nano-array, embodiment three1.33Ni0.67P4O12The Co of C nano array and comparative experiments preparation2P4O12-C@
The Raman spectrogram of CC nano-array is as shown in figure 3, partial enlarged view is as shown in Figure 4；As can be seen from Fig., in addition to carbon cloth substrate
In~1360cm-1With~1586cm-1The peak D and the peak G of generation.In 578cm-1, 719cm-1And 916cm-1The peak at place is attributed to
[P4O12]4-The stretching vibration of ion illustrates deviation phosphate rather than phosphide by being formed after low temperature phosphorylation reaction.
Scanning electron microscope (SEM) figure of blank carbon cloth is as shown in Figure 5.
High power scanning electron microscope (SEM) figure such as Figure 10 of CoNi (4:1)-ZIF nano-array prepared by embodiment one
It is shown, low power scanning electron microscope (SEM) figure such as Figure 11 institute of CoNi (4:1)-ZIF nano-array prepared by embodiment one
Show, high power scanning electron microscope (SEM) figure of CoNi (8:1)-ZIF nano-array prepared by embodiment two is as shown in figure 8, reality
Low power scanning electron microscope (SEM) figure of CoNi (8:1)-ZIF nano-array of the preparation of example two is applied as shown in figure 9, embodiment
High power scanning electron microscope (SEM) figure of CoNi (2:1)-ZIF nano-array of three preparations is as shown in figure 12, and embodiment three is made
Low power scanning electron microscope (SEM) figure of standby CoNi (2:1)-ZIF nano-array is as shown in figure 13, comparative experiments preparation
High power scanning electron microscope (SEM) figure of CoNi (1:0)-ZIF nano-array is as shown in fig. 6, CoNi prepared by comparative experiments
Low power scanning electron microscope (SEM) figure of (1:0)-ZIF nano-array passes through as shown in fig. 7, compared with blank carbon cloth (Fig. 5)
It crosses after co-precipitation, grown one layer of regular shape and nano-array of uniform size, and the CoNi synthesized in carbon cloth surfaces
(n)-ZIF be in 2D laminated structure, a length of 1.5 μ m thick of piece is about 100-150nm, and surface is smooth, each nm wall it
Between have very large space, this is beneficial to electrolyte and permeates between catalyst.
Co prepared by embodiment one1.6Ni0.4P4O12High power scanning electron microscope (SEM) figure of-C@CC nano-array is such as
Shown in Figure 18, the Co of the preparation of embodiment one1.6Ni0.4P4O12Low power scanning electron microscope (SEM) figure of-C@CC nano-array is such as
Shown in Figure 19, the Co of the preparation of embodiment two1.78Ni0.22P4O12High power scanning electron microscope (SEM) figure of-C@CC nano-array
As shown in figure 16, Co prepared by embodiment two1.78Ni0.22P4O12The low power scanning electron microscope (SEM) of-C@CC nano-array
Figure is as shown in figure 17, Co prepared by embodiment three1.33Ni0.67P4O12High power scanning electron microscope (SEM) figure of C nano array
As shown in figure 20, Co prepared by embodiment three1.33Ni0.67P4O12Low power scanning electron microscope (SEM) figure of C nano array is such as
Shown in Figure 21, the Co of comparative experiments preparation2P4O12High power scanning electron microscope (SEM) figure such as Figure 14 of-C@CC nano-array
It is shown, the Co of comparative experiments preparation2P4O12Low power scanning electron microscope (SEM) figure of-C@CC nano-array is as shown in figure 15,
From in figure 14~21 as can be seen that can be very good to maintain original presoma by the catalyst formed after Low Temperature Solid-Phase phosphatization
Pattern, but surface becomes more coarse, and the width of piece narrows, and the distance between piece and piece are further enlarged, and is conducive to electricity
The quick release for solving the bubble of infiltration and generation of the liquid between catalyst, to enhance OER catalytic performance.
Co prepared by embodiment one1.6Ni0.4P4O12The EDS figure of-C@CC nano-array is as shown in figure 22, from containing for each element
Amount is it can be seen that contain a large amount of phosphate in the catalyst.
Co prepared by embodiment one1.6Ni0.4P4O12The TEM figure of-C@CC nano-array as shown in figure 23, can from figure
Out, the Co of formation1.6Ni0.4P4O12The surface of-C is porous and is made of many inside little particle interconnected, the result
Show that Phosphorylation events can make the more active sites of catalyst exposure, this will promote the raising of OER performance.
Co prepared by embodiment one1.6Ni0.4P4O12The HRTEM figure of-C CC nano-array as shown in figure 24, can be with from figure
Find out, Co prepared by embodiment one1.6Ni0.4P4O12The SAED figure of-C@CC nano-array such as Figure 25, as can see from Figure 24 its
Spacing of lattice is 0.299nm, the Co prepared according to Figure 26 in experiment1.6Ni0.4P4O12C nano composite material crystallinity is very
Good, crystal is grown along (- 113) crystal face.
Co prepared by embodiment one1.6Ni0.4P4O12The angle of elevation annular dark of-C CC nano-array-scanning transmission electricity
Son scanning transmission microscope photo as in is as shown in figure 26, and as can be seen from Figure 26, Co, Ni, tetra- kinds of elements of P and O are uniformly distributed
On carbon skeleton, while this also illustrates this tests successfully to prepare Co1.6Ni0.4P4O12- C@CC nano-array.
Co prepared by embodiment one1.6Ni0.4P4O12- C@CC nano-array, Co prepared by embodiment two1.78Ni0.22P4O12-
Co prepared by C@CC nano-array, embodiment three1.33Ni0.67P4O12The Co of C nano array and comparative experiments preparation2P4O12-C@
CC nano-array and blank carbon cloth, business IrO2Linear scan (LSV) curve of@CC is as shown in figure 27, and Tafel slope figure is such as
Shown in Figure 28, effective active area-graph is as shown in figure 29, and AC impedance figure is as shown in figure 30, wherein " 1 " represents
Co1.6Ni0.4P4O12- C, " 2 " represent Co1.78Ni0.22P4O12- C, " 3 " represent Co1.33Ni0.67P4O12- C, " 4 " represent Co2P4O12-
C, " 5 " represent IrO2@CC, " 6 " represent CC.By Figure 27, blank carbon cloth poor performance known to 28 carries out gold compared with one-component
When can effectively improve the OER activity of catalyst after belonging to doping, but adulterating excessive, the performance of catalyst declines instead, wherein
The Co formed when Co/Ni is 4:11.6Ni0.4P4O12- C@CC nano-composite catalyst has optimal catalytic performance, in electric current
Density is 10mA/cm2When, overpotential is only 230mV, slope 51.1mV/dec, less than the slope of remaining sample, even lower than
Business IrO2@CC, this illustrates Co1.6Ni0.4P4O12- C@CC is 10mA/cm in current density2When left and right, current density is with overvoltage
Rising increase it is the rapidest, show Co1.6Ni0.4P4O12- C@CC is urged during catalytic electrolysis aquatic products hydrogen compared to others
Agent has faster oxygen evolution kinetic process.As shown in Figure 29, Co1.6Ni0.4P4O12The electrochemistry effective active area of-C@CC
For 17.3mF/cm2, it is much larger than Co1.78Ni0.22P4O12-C(11.2mF/cm2), Co1.33Ni0.67P4O12-C(7.4mF/cm2) and
Co2P4O12-C(10.2mF/cm2), illustrate Co1.6Ni0.4P4O12- C@CC has more active sites in solid liquid interface, this master
If since there is catalyst porous structure to determine.It is possible to observe from figure 30 that the Co in all catalyst1.6Ni0.4P4O12-C@CC
Charge-transfer resistance it is minimum, therefore driving voltage needed for the material charge migration is small, i.e. Co1.6Ni0.4P4O12CC nanometers of battle arrays of-C@
Column attrition voltage is minimum, this is also Co1.6Ni0.4P4O12The optimal reason of-C@CC nanocomposite OER performance.
Co prepared by embodiment one1.6Ni0.4P4O12The multistep current course of-C@CC nanocomposite is as shown in figure 31,
Figure 32 is Co prepared by embodiment one1.6Ni0.4P4O12- C@CC nano-array carries out electrocatalytic decomposition elutriation in alkaline electrolyte
The polarization curve curve graph of the circle of oxygen reaction cycle 1000 front and back, wherein " ■ " represents 1 circle of circulation, "●" represents 1000 circle of circulation,
Figure 33 is electric current versus time curve figure under constant voltage, can as seen from the figure, material electricity after long-time is tested
Current density decline seldom, shows that the catalyst has excellent stability.
Co after 1000 circle CV of circulation1.6Ni0.4P4O12The SEM (1 μm) of-C@CC nano-array sample as shown in figure 34, TEM
Scheme (50nm) as shown in figure 35, the Co after 1000 circle CV of circulation1.6Ni0.4P4O12The HRTEM of-C@CC nanocomposite schemes
(2nm) as shown in figure 36, scheming can be seen that the catalyst surface after long-time is tested from SEM, TEM has slight change,
This shows that the composition of catalyst during OER changes, and phosphate transfection turns to other substances and makes internal nanometer
Generation electrochemical etching is exposed in grain.Further by HRTEM figure as can be seen that its spacing of lattice be 0.188nm,
0.483nm and 0.189nm, 0.164nm correspond respectively to (107) of NiOOH, (131) of (001) crystal face and CoOOH,
(104) crystal face, should be the result shows that the composition of the catalyst changes after long-time OER, and NiOOH and CoOOH are only
Real catalytic active substance.
In order to further analyze the existence form of sample, Co prepared by embodiment one1.6Ni0.4P4O12CC nanometers of-C@
XPS Comparative map of the array before and after OER test, as shown in figs. 37-39, Co element swarming figure is as shown in figure 37, from Figure 37
As can be seen that the valence state of Co changes after OER, gradated by the Co ion of original divalent as higher price
CoOOH.Figure 38, Figure 39 are the swarming of P and O respectively as a result, as can be seen from the figure after long-time is tested, the peak of P and O
Type weakens, and the peak of M-P-O completely disappears, and the peak of M-O and M-OH account for leading, which also shows catalyst after OER
Composition changes.
Co after 1000 circle CV of circulation1.6Ni0.4P4O12The Raman of-C@CC nano-array sample compares spectrogram such as Figure 40 institute
Show, it can be seen from the figure that [P after OER4O12]4-In 600-1000cm-1The peak at place completely disappears, in 503,590 and 473cm-1Place generates new peak and corresponds respectively to CoOOH and NiOOH, and the rear catalyst composition which further demonstrates OER becomes
Change is converted into CoOOH and NiOOH, as real catalytic active substance, matches with above-mentioned other characterization results.
It can be concluded that, successfully it is prepared for that there is height using the present embodiment according to above-mentioned characterization result and electro-chemical test
Electro catalytic activity, and the Co of low cost1.6Ni0.4P4O12- C@CC nanocomposite.The catalyst is parsed in electro-catalysis moisture
In oxygen experimental applications, have excellent catalytic properties.
Claims (10)
1. a kind of preparation method for the cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate, it is characterised in that should
Method sequentially includes the following steps:
One, by the carbon cloth successively supersound washing in acetone, ethyl alcohol and aqueous solution, then in dense HNO3Middle supersound washing, is washed with water
It washs, dries, the carbon cloth that obtains that treated；
Two, by Co (NO3)2·6H2O and Ni (NO3)2·6H2O is distributed in deionized water, and magnetic agitation is uniform, is labeled as solution
A；In deionized water by 2-methylimidazole dispersion, solution B is poured into molten under continuing magnetic force stirring action labeled as solution B
In liquid A, stirring obtains mixed solution labeled as solution C；
Three, by step 1, treated that carbon cloth is immersed in the solution C that step 2 obtains, and continuously stirs 2~6h at room temperature, so
Carbon cloth is taken out afterwards, is cleaned repeatedly with deionized water, then vacuum constant temperature is dry, obtains being supported on the bimetallic MOF on carbon cloth
Presoma；
Four, the bimetallic MOF presoma being supported on carbon cloth for obtaining step 3 is put into Al2O3In porcelain boat, which is placed on
At tube furnace downstream, another is equipped with NaH2PO2·H2The porcelain boat of O is placed on the upstream end of tube furnace, heats up under an argon atmosphere
To 300~450 DEG C, 2~4h is kept the temperature, then cooled to room temperature, obtains solid preformulation；
Five, the solid preformulation dispersion obtained step 4 in deionized water, stirs 30~60min, centrifuge washing；
Six, step 5 is repeated as many times, then with ethanol washing, centrifugation, it is dry, obtain Co2-xNixP4O12The nano combined material of-C@CC
Material completes preparation；Wherein 0.11 ﹤ x ﹤ 2.
2. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that in dense HNO in step 13Middle 4~4.5h of supersound washing.
3. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that Co (NO in step 2 solution A3)2·6H2The concentration of O is 25~50mmol/L.
4. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that Ni (NO in step 2 solution A3)2·6H2The concentration of O is 2.9~25mmol/L.
5. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that the concentration of 2-methylimidazole is 0.1~0.4mol/L in step 2 solution B.
6. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that the volume ratio of step 2 solution A and solution B is 1: 1.
7. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that vacuum constant temperature drying temperature is 60~62 DEG C in step 3, drying time > 10h.
8. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that NaH in step 42PO2·H2The quality of O is 1~2g.
9. a kind of system of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation Method, it is characterised in that it is 2~5 DEG C/min that heating rate is controlled in step 4.
10. a kind of cobalt nickel bimetal metaphosphate nano-array being supported in carbon cloth substrate according to claim 1
Preparation method, it is characterised in that repeat step 5 4~5 times in step 6.
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