CN109161923A - Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its electro-catalysis application - Google Patents
Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its electro-catalysis application Download PDFInfo
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- CN109161923A CN109161923A CN201811307926.XA CN201811307926A CN109161923A CN 109161923 A CN109161923 A CN 109161923A CN 201811307926 A CN201811307926 A CN 201811307926A CN 109161923 A CN109161923 A CN 109161923A
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- carbon nanotube
- cobalt
- ferro
- hydrotalcite
- acrylic
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 54
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 11
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 10
- 239000002114 nanocomposite Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 26
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000004448 titration Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- MNEWTQVKBYXSSK-UHFFFAOYSA-N formamide;iron Chemical compound [Fe].NC=O MNEWTQVKBYXSSK-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 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
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to the catalytic applications that a kind of carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its gained compound react electrolyzed alkaline water Oxygen anodic evolution.Divalent cobalt and ferric iron are dissolved in the mixed solution of the formamide containing carboxylic carbon nano-tube and water, with dilute alkaline soln direct titration, carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece complex catalyst has been made in the ultra-thin ferro-cobalt acrylic/hydrotalcite-like nano piece of growth in situ in carboxylic carbon nano-tube substrate.The method reduce removing houghite steps, prevent the aggregation of acrylic/hydrotalcite-like nano piece, increase the active site of catalyst, the synergistic effect of acrylic/hydrotalcite-like nano piece and carbon nanotube in terms of electro-catalysis is given full play to, reduce the overpotential of oxygen evolution reaction, it is improved to oxygen evolution reaction electrocatalysis characteristic, is of great significance to novel oxygen evolution reaction catalysts are developed.
Description
Technical field:
The invention belongs to novel energy resource material technology and electro-catalysis technical fields, and in particular to carbon nanotube/ferro-cobalt class neatly
The preparation method of stone nanometer sheet compound further includes electro-catalysis application of the catalyst in the reaction of electrolyzed alkaline water Oxygen anodic evolution
Background technique:
As the environmental problems such as the global warming caused by fossil fuel are prominent, researcher throws a large amount of energy
Enter in the exploitation and efficient storage and conversion to new energy.And the analysis being related in new energy storage and conversion process
Oxygen reaction (OER) process is slow, is to hinder fuel cell, water-splitting energy-storage system (OER), too oxygen energy fuel synthesis (OER) are answered
With one of the main problem in popularization.In these energy storages and conversion equipment, the catalyst for OER have noble metal Ru,
Ir and its oxide.For noble metal catalyst because its earth reserves is small, the factors such as expensive limit it in terms of new energy
Using.And these noble metal catalyst stability are poor, cannot be used for a long time.Therefore, research and develop it is a kind of just with production, non-expensive
Metal, the OER that can be recycled catalyst become research hotspot.
The material of iron-cobalt-nickel base includes the hydroxide of iron-cobalt-nickel, oxide, has good OER catalytic activity.Wherein,
Ferro-cobalt double-metal hydroxide is also known as ferro-cobalt houghite, is denoted as CoFe-LDH, is a kind of two-dimensional layer material, and composition is logical
Formula is represented by [Co1-x 2+Fex 3+(OH)2]x+(An-)x/n·mH2O, it is equal with charge therewith by positively charged hydroxide layer
The interlayer anion of weighing apparatus forms.Since reserves of the ferro-cobalt in the earth are very rich, the nano material of ferro-cobalt base, especially
CoFe-LDH presents good application prospect in energy conversion and field of storage.However in actual application, CoFe-
LDH catalyst material there is also specific surface areas small, poorly conductive, the disadvantages of easily aggregation and stability are poor.In order to overcome above lack
LDH is removed into the thin slice (LDHNS) of single-layer or multi-layer by point, researcher, to improve its specific surface area and active site, together
When the materials such as some carbon materials such as graphene (GR) and carbon nanotube (CNT) and LDH nanometer sheet are compound, improve composite material
Electric conductivity prevents LDH from assembling, improves its performance.Carbon nanotube also known as Baji-tube are a kind of with special construction (radial dimension
For nanometer scale, axial dimension is micron dimension, and pipe both ends are substantially all sealing) One-dimensional Quantum material.Carbon nanotube master
Several layers to tens of layers of coaxial round tube is made of the carbon atom of hexagonal arrangement.The distance being kept fixed between layers,
About 0.34nm, diameter are generally 2~20nm.The specific surface area (~1315m of carbon nanotube tool superelevation2/ g) and excellent conduction
Property, the charge transfer and mass-transfer efficiency in electrocatalytic reaction can be greatly improved.And the carbon nanotube that carboxylated is later
(HCNTs) negatively charged, the other static buildup of molecular level can be carried out with positively charged LDH nanometer sheet, the transition in LDHNS can be made
Metal catalytic center and conductive sp2Hydbridized carbon atoms are in close contact, and greatly shorten the diffusion length of electrolyte.Although by quiet
LDH and HCNTs is carried out compound the problems such as can solve LDH material conductivity difference and aggregation by electricity assembling, but preparation method relates to
And LDH removing, electrostatic assembly the problems such as.
In order to simplify the preparation method of catalyst, the enforceability of industrialized production is improved, the present invention is by divalent cobalt and three
Valence iron is dissolved in the formamide of HCNTs and the mixed solution of water, and with diluted alkaline direct titration, growth in situ is super in HCNTs substrate
Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound (LDHNS/HCNTs) VPO catalysts are made in thin CoFe-LDHNS.Mesh
It is preceding that the research of LDHNS/HCNTs VPO catalysts and the catalyst for electrolyzed alkaline water anode OER is prepared using this one-step method
It has not been reported.
The present invention use using the carbon nanotube of carboxylated as substrate, the growth in situ in the mixed solution of formamide and water
Ultra-thin CoFe-LDHNS avoids the strip step of LDH, prevents the aggregation of LDHNS, increases the active sites of catalyst
Point, reduces the overpotential of OER, to improve its OER electrocatalysis characteristic.Elctro-catalyst obtained by this method gives full play to
Synergistic effect of the LDHNS and HCNTs in terms of electro-catalysis is of great significance to novel oxygen evolution reaction catalysts are developed.
Summary of the invention:
For aggregation existing for current preparation LDH compound, that partial size is big, particle size distribution range is wide, specific surface area is small etc. is existing
There are the deficiency of technology and the demand of this field research and application, an object of the present invention to be to provide a kind of carbon nanotube/cobalt
The preparation method of iron acrylic/hydrotalcite-like nano piece compound, it is characterised in that in formamide-water mixing of the carbon nanotube of carboxylated
It is made in solution through co-precipitation one-step method, comprising the following specific steps
The carbon nanotube for taking a certain amount of carboxylated is denoted as HCNTs, and ultrasonic disperse is in the mixed solvent of 50mL formamide and water
In, make 0.4~0.8mg/mL of its concentration, Fe(NO3)39H2O and cabaltous nitrate hexahydrate is added by certain mol proportion, makes total gold
Category ion concentration is 6mmol/L, and stirring 1h is completely dissolved metal salt, under conditions of being vigorously stirred, is with concentration
It is 8.5~9.5 that the formamide and water mixed solution of the sodium hydroxide of 0.14mol/L, which are slowly titrated to reaction solution pH, by reaction solution
It is multiple to get ferro-cobalt houghite/carbon nanotube with deionized water and ethanol washing 3 times respectively after 4000rpm centrifuge separation
Object is closed, LDHNS/HCNTs is denoted as.
Wherein the molar ratio of Fe(NO3)39H2O and cabaltous nitrate hexahydrate is 1:2；The mixed solvent or molten of formamide and water
The percent by volume of formamide is 40~100% in liquid；Ferro-cobalt class in gained ferro-cobalt houghite/carbon nanotube nanocomposite
The size of hydrotalcite nano piece is less than 100nm, and thickness is less than 2nm, and vertical-growth is in carbon nanotube.
The second object of the present invention is to provide a kind of carbon nanotube that one-step method is prepared/ferro-cobalt acrylic/hydrotalcite-like nano piece
The catalytic applications that compound reacts electrolyzed alkaline water Oxygen anodic evolution.
The present invention is using the carbon nanotube of carboxylated as substrate, and growth in situ is ultra-thin in the mixed solution of formamide and water
CoFe-LDHNS avoids the strip step of LDH, increases the active site of catalyst, reduces the overpotential of OER, thus
Improve its electrocatalysis characteristic.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) step of the present invention is when preparation carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound method, not only
It solves the problems, such as LDHNS aggregation, poorly conductive, and avoids the strip step of LDH, increase the close of LDHNS and CNT
Contact, to improve the electric conductivity and active catalyst sites of catalyst, has given full play to LDHNS and CNT in terms of electro-catalysis
Excellent properties；
2) the resulting catalyst of preparation method of the present invention be base metal composite material, it is raw materials used be easy to buy and
Preparation, resourceful and price is lower, easily operated, convenient for large-scale production；With preferable OER activity, good stabilization
Property, constant voltage is imposed in 0.1mol/L KOH electrolyte, the current density of experience 9h catalyst still keeps 91%, more at present
Base metal/non-metallic catalyst catalytic activity of research report has significant advantage.
Detailed description of the invention:
Fig. 1 is the XRD spectrum of 2 gained LDH/HCNTs of 2 gained LDHNS/HCNTs compound of embodiment and comparative example.
Fig. 2 is that the TEM of 2 gained LDHNS/HCNTs compound of embodiment schemes.
Fig. 3 is 2 gained LDHNS/HCNTs compound of embodiment, 1 gained LDH of comparative example, 2 gained LDH/HCNTs of comparative example
Compound and RuO2The linear volt-ampere curve figure of the OER of modified glassy carbon electrode.
Fig. 4 is the corresponding Tafel curve of each linear voltammetric scan curve of item obtained in reality Fig. 2.
Fig. 5 is 2 gained LDHNS/HCNTs compound of embodiment in 10mA/cm2Current decay curve under corresponding current potential
Figure.
Fig. 6 sweeps fast obtain by difference for 2 gained LDHNS/HCNTs compound of embodiment and 2 gained LDH/HCNTs of comparative example
Electric double layer capacitance C outdl。
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in aqueous solution of the 50mL containing 50% formamide, keeps its dense
Degree is 0.4mg/mL, and cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto by the molar ratio of 2:1, keeps total metal ion dense
6mmol/L is spent, stirring 1h is completely dissolved metal salt, under intense agitation, with containing for the sodium hydroxide of 0.14mol/L
The pH that the aqueous solution of 50% formamide is slowly titrated to reaction solution is 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively
With deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite, it is denoted as LDHNS/HCNTs-
0.4。
Embodiment 2:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in aqueous solution of the 50mL containing 50% formamide, keeps its dense
Degree is 0.6mg/mL, and cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto by the molar ratio of 2:1, keeps total metal ion dense
6mmol/L is spent, stirring 1h is completely dissolved metal salt, under intense agitation, with containing for the sodium hydroxide of 0.14mol/L
The pH that the aqueous solution of 50% formamide is slowly titrated to reaction solution is 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively
With deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite, it is denoted as LDHNS/HCNTs-
0.6。
Embodiment 3:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in aqueous solution of the 50mL containing 50% formamide, keeps its dense
Degree is 0.8mg/mL, and cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto by the molar ratio of 2:1, keeps total metal ion dense
6mmol/L is spent, stirring 1h is completely dissolved metal salt, under intense agitation, with containing for the sodium hydroxide of 0.14mol/L
The pH that the aqueous solution of 50% formamide is slowly titrated to reaction solution is 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively
With deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite, it is denoted as LDHNS/HCNTs-
0.8。
Embodiment 4:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in aqueous solution of the 50mL containing 60% formamide, keeps its dense
Degree is 0.6mg/mL, and cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto by the molar ratio of 2:1, keeps total metal ion dense
6mmol/L is spent, stirring 1h is completely dissolved metal salt, under intense agitation, with containing for the sodium hydroxide of 0.14mol/L
The pH that the aqueous solution of 50% formamide is slowly titrated to reaction solution is 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively
With deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite, it is denoted as LDHNS/HCNTs-
60。
Embodiment 5:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in aqueous solution of the 50mL containing 80% formamide, keeps its dense
Degree is 0.6mg/mL, and cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto by the molar ratio of 2:1, keeps total metal ion dense
6mmol/L is spent, stirring 1h is completely dissolved metal salt, under intense agitation, with containing for the sodium hydroxide of 0.14mol/L
The pH that the aqueous solution of 50% formamide is slowly titrated to reaction solution is 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively
With deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite, it is denoted as LDHNS/HCNTs-
80。
Comparative example 1:
Cabaltous nitrate hexahydrate and nine nitric hydrates are added by the molar ratio of 2:1 into aqueous solution of the 50mL containing 50% formamide
Iron makes its concentration 6mmol/L, and stirring 1h makes it completely dissolved, under intense agitation, with the hydroxide of 0.14mol/L
The pH that the aqueous solution containing 50% formamide of sodium is slowly titrated to reaction solution is 8.5~9.5, reaction solution 4000rpm centrifuge separation
Afterwards, respectively with deionized water and ethanol washing 3 times to get ferro-cobalt acrylic/hydrotalcite-like nano piece, it is denoted as LDHNS.
Comparative example 2:
It takes the carbon nanotube ultrasonic disperse of a certain amount of carboxylated in 50mL water, makes its concentration 0.6mg/mL, by 2:1
Molar ratio cabaltous nitrate hexahydrate and Fe(NO3)39H2O are added thereto, make total concentration of metal ions 6mmol/L, stirring 1h makes
Metal salt is completely dissolved, and under intense agitation, is slowly titrated to reaction solution with the aqueous solution of the sodium hydroxide of 0.14mol/L
PH be 8.5~9.5, after reaction solution 4000rpm centrifuge separation, respectively with deionized water and ethanol washing 3 times to get ferro-cobalt class
Hydrotalcite/carbon nanotube nanocomposite, is denoted as LDH/HCNTs.
Fig. 1 is the XRD spectrum of 2 gained LDH/HCNTs of 2 gained LDHNS/HCNTs compound of embodiment and comparative example.Such as figure
Shown, there is LDH-NO in LDHNS/HCNTs and LDH/HCNTs3Characteristic peak, respectively 003 (11.5 °), 006
(18.8 °), 012 (34.2o) illustrate to generate NiFe-LDH stratified material in two kinds of compounds, in addition in XRD spectrum
All there is the diffraction maximum of CNT at 24 ° or so.But there is apparent difference again between the two, due to containing in mixed solution
Formamide has played its swelling and inhibiting effect, and the LDHNS in compound LDHNS/HCNTs is rendered as ultrathin nanometer piece, and
It cannot accumulate in parallel, but growth in situ thus results in hydrotalcite nano piece in carbon nano tube surface in vertical manner
Each characteristic diffraction peak obviously broadens, and shows its ultra-thin characteristic, this characteristic is conducive to it and plays OER catalytic activity.
Fig. 2 is the transmission electron microscope picture of 2 gained LDHNS/HCNTs nano-complex of embodiment.It can be seen from the figure that due to
The presence of formamide in reaction medium, growth in situ LDHNS on carboxylic carbon nano-tube present ultra-slim features, nanometer sheet
Size be less than 100nm, thickness is less than 2mn, and vertical-growth is in carbon nano tube surface.It is concluded that: the carbon of carboxylated
Nanotube is substrate, and the carboxyl functional group on surface is by metal species Co2+And Fe3+After absorption is fixed, with the slow drop of lye
It is fixed to be added, in the ultra-thin LDHNS of carbon nano tube surface growth in situ.It is ultra-thin due to the swelling and inhibiting effect of formamide
LDHNS can not accumulate in parallel, to form ultra-thin nanometer sheet in carbon nano tube surface in vertical manner, eventually lead to shape
At LDHNS/HCNTs compound.
Embodiment 6:
200 μ L ethyl alcohol and 20 μ L are dispersed by 20mg embodiment 2, comparative example 1 and the resulting catalyst of comparative example 2 respectively
In 0.5% Nafion solution, after ultrasound mixes solution, takes 3 μ L slurry drops to be applied on glass-carbon electrode, pressed after it is completely dried
Piece measures its OER electrocatalysis characteristic on CHI660D electrochemical workstation；
Above-mentioned electrocatalysis characteristic test is to be saturated Hg/HgO electrode as reference electrode, and Pt electrode is to electrode, and sweeping speed is
10mV/s, electrolyte are 0.1M KOH.Tafel slope can be calculated by E=a+b log J.
Wherein E is overpotential, and J is current density, and a and b are respectively constant, and wherein b is Tafel slope.
Embodiment 7:
It disperses 200 respectively by 2 gained LDHNS/HCNTs of 20mg embodiment and 2 gained LDH/HCNTs catalyst of comparative example
In μ L ethyl alcohol and the Nafion solution of 20 μ L 0.5%, after ultrasound mixes solution, 3 μ L slurry drops is taken to be applied on glass-carbon electrode,
Its CV curve is measured on CHI660D electrochemical workstation after it is completely dried.To sweep speed as abscissa, 0.25V is corresponding
CV current potential absolute value of the difference is ordinate, obtains electric double layer capacitance C by slopedl；
To be saturated Hg/HgO electrode as reference electrode, Pt electrode is to electrode, surface sweeping side for above-mentioned electrocatalysis characteristic test
To for from negative potential to positive electricity bit scan, electrolyte is 0.1M KOH.
Fig. 3 is 2 gained LDHNS/HCNTs compound of embodiment, 1 gained LDH of comparative example, 2 gained LDH/HCNTs of comparative example
And RuO2The linear volt-ampere curve figure of the OER of modified glassy carbon electrode.As shown, the OER of LDHNS/HCNTs modified electrode is originated
Overpotential is 180mV, hence it is evident that 340mV and RuO lower than LDH2330mV, and LDH/HCNTs catalyst is corresponding originated electricity
330mV is down to compared to LDH in position.Meanwhile when current density is 10mA/cm2When, LDHNS/HCNTs, LDH/HCNTs, RuO2With
The corresponding overpotential of LDH respectively may be about 250,420,420 and 520mV.It can clearly be seen that in the carbon nanotube substrate of carboxylated
After upper in-situ preparation CoFe-LDHNS, significantly reduce its overpotential, this be mainly due to compound HCNTs with it is ultra-thin
After LDHNS is compound, LDHNS does not assemble, and sufficiently exposes its active site, improve catalyst permeability and
Conductive capability is conducive to the evolution of oxygen molecule and the transmitting of electronics, substantially improves the OER catalytic performance of catalyst.
Fig. 4 is the Tafel slope that each curve negotiating is calculated in Fig. 3.As shown, in respective polarization section,
LDH、LDH/HCNTs、RuO2Tafel slope with LDHNS/HCNTs be respectively 105mV/dec, 79mV/dec, 73mV/dec and
46mV/dec.Low Tafel slope shows high electron transfer rate.LDH has larger Tafel slope, in compound carboxylated
After carbon nanotube, the Tafel slope of LDH/HCNTs decreases, and in the medium containing formamide, LDHNS is raw in situ
It grows on the surface HCNTs, therefore LDHNS/HCNTs presents minimum Tafel slope, even lower than noble metal RuO2's
Tafel slope shows that LDHNS/HCNTs has most fast electron transfer rate.
Fig. 5 is 2 gained LDHNS/HCNTs compound modified glassy carbon electrode of embodiment in 10mA/cm2Under constant voltage test
Figure.As shown, by the continuous OER test process of 9h, the OER current density of LDHNS/HCNTs is only had occurred less than 8%
Decaying, this is mainly due to the lasting precipitation of oxygen bubble, constantly impact electrode surface LDHNS/HCNTs catalyst and caused by
It is micro to fall off, it can be seen that LDHNS/HCNTs repairs electrode and shows good OER catalytic stability in alkaline solution, has
Longer service life.
Fig. 6 is the electric double layer capacitance C of 2 gained LDHNS/HCNTs compound of embodiment, 2 gained LDH/HCNTs of comparative exampledl。
As shown, compared with the LDH/HCNTs synthesized in an aqueous medium, the C of LDHNS/HCNTs catalystdlIncrease 0.4mF/
cm2, illustrate that the LDHNS/HCNTs synthesized in the medium containing formamide has more compared to the LDH/HCNTs synthesized in water
Big effective active surface area, this result are consistent with transmission electron microscope and LSV result.High effective electroactive area is further explained
The reason of LDHNS/HCNTs good OER is illustrated.
Claims (3)
1. a kind of carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method, it is characterised in that received in carboxylated carbon
It is made in the formamide of mitron-water mixed dispersion liquid through co-precipitation one-step method, the specific steps are as follows:
The carbon nanotube for taking a certain amount of carboxylated, is denoted as HCNTs, ultrasonic disperse in the in the mixed solvent of 50mL formamide and water,
Make 0.4~0.8mg/mL of its concentration, Fe(NO3)39H2O and cabaltous nitrate hexahydrate be added by certain mol proportion, make total metal from
Sub- concentration is 6mmol/L, and it is 0.14mol/L's with concentration under conditions of being vigorously stirred that stirring 1h, which is completely dissolved metal salt,
It is 8.5~9.5 that the formamide and water mixed solution of sodium hydroxide, which are slowly titrated to reaction solution pH, and reaction solution 4000rpm is centrifuged
After separation, it is denoted as respectively with deionized water and ethanol washing 3 times to get ferro-cobalt houghite/carbon nanotube nanocomposite
LDHNS/HCNTs。
2. a kind of carbon nanotube according to claim 1/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method, special
Sign is that the molar ratio of Fe(NO3)39H2O and cabaltous nitrate hexahydrate is 1:2；First in the mixed solvent or solution of formamide and water
The percent by volume of amide is 40~100%；Ferro-cobalt houghite in gained ferro-cobalt houghite/carbon nanotube nanocomposite
The size of nanometer sheet is less than 100nm, and thickness is less than 2nm, and vertical-growth is in carbon nanotube.
3. a kind of carbon nanotube according to claim 1/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method, special
Sign is that the ferro-cobalt houghite/carbon nanotube nanocomposite obtained using the preparation method can be used for electrolyzed alkaline water anode
Analyse oxygen catalysis reaction.
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