CN110354862A - The method that nickel foam stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode - Google Patents
The method that nickel foam stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode Download PDFInfo
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- CN110354862A CN110354862A CN201910750026.0A CN201910750026A CN110354862A CN 110354862 A CN110354862 A CN 110354862A CN 201910750026 A CN201910750026 A CN 201910750026A CN 110354862 A CN110354862 A CN 110354862A
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- cerium ion
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 239000001301 oxygen Substances 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 27
- 239000006260 foam Substances 0.000 title claims abstract description 27
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 23
- 239000011029 spinel Substances 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 238000004458 analytical method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 27
- -1 cerium ion Chemical class 0.000 claims abstract description 22
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HDXXSUQVQKJEBI-UHFFFAOYSA-N carbonic acid;cerium Chemical compound [Ce].OC(O)=O HDXXSUQVQKJEBI-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 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
- 230000003760 hair shine Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/33—
-
- B01J35/60—
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
-
- 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 discloses the method that nickel foam stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode, it is respectively source of iron using Nickelous nitrate hexahydrate and Fe(NO3)39H2O and nickel source, six nitric hydrate ceriums are auxiliary synthetics, urea is hydrolytic reagent, nickel foam for conducting base, using hydro-thermal method, on nickel foam conducting base surface, a step fabricated in situ three-dimensional nickel-ferric spinel nano lamellar material.Due to the surface coordination effect of cerium ion in the synthesis process, form relatively thin nickel-ferric spinel nano lamellar material, and the Lacking oxygen number of material surface increases, increase so as to cause the ligancy reduction of catalytic active center (nickel and iron), activity, greatly increases the electro-catalysis analysis oxygen ability of nickel-ferric spinel nano lamellar material.
Description
Technical field
The invention belongs to material science and technology field and electrocatalytic decomposition water hydrogen preparation fields, and in particular to nickel foam matrix table
The method that face cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode.
Background technique
With the increase of population in the world, the consumption of fossil fuel and upcoming climate change, these are very important
Energy security problem have stimulated the research and development of renewable energy system.A kind of effective solution scheme is exploitation electrochemistry
Water decomposition technique, by reproducible energy source use in clean fuel.However, oxygen release reaction (OER) is the key that water decomposition
Step, and be also the bottleneck of water decomposition efficiency, i.e. the slow dynamics of OER limits the gross efficiency of water decomposition.Past
In decades, people are dedicated to developing high activity, durable and inexpensive elctro-catalyst, your gold be based in the prior art to replace
Catalyst (such as RuO of category2Or IrO2).So far, in promising substitute, Ni-Fe layered double-hydroxide (NiFe
LDHs, chemical general formula are [Ni2+ 1-xFe3+ x(OH)2]q+(An−)q/n·yH2O) have at alkaline environment (pH:13-14) most fast
Intrinsic electro catalytic activity, this have benefited from they sandwich and with atom level dispersion active metal.However, NiFe
LDHs is that the layer structure stacked causes its active site (Ni and Fe) inabundant as the greatest drawback of elctro-catalyst
It utilizes, and NiFe LDHs electric conductivity is poor, the electronics transfer being unfavorable between electrode, catalyst and reactant (product).Closely
Next, ultrasonic wave removing is the thickness that NiFe LDHs is thinned and the effective ways for increasing active site quantity, but its shortcoming is that is consumed
When and electrode production process it is cumbersome, and nanometer sheet stack again or the electrical contact between nanometer sheet and glass-carbon electrode (GCE) not
It is good, cause catalytic efficiency low.In addition, compared with directly loading elctro-catalyst on GCE, in three-dimensional (3D) porous support of Ni foam
Surface, the porous elctro-catalyst of the 3D being prepared in situ will have higher catalyst loadings and better electrode contact performance, can
Significantly increase catalytic activity.However, design, the thickness of regulation activity material are still more difficult in 3D porous scaffold surface.It is urging
The modified aspect in agent surface has the low coordination of more Lacking oxygens, surface metal and more metallic suspension keys, is to improve catalyst
Analyse the key of oxygen performance.
Cerium belongs to rare earth element, has unique 4f orbital electron, biggish atomic magnetic moment, biggish spin and track effect
It answers, easily forms different coordination modes from most elements and multivalent state compound.In addition, compared with Ni and Fe, since electricity is negative
Property Ce(1.12) lower (< Fe(1.83) < Ni(1.91)), Ce may be coordinated with the oxygen on material surface in the synthesis process.
Therefore, by adding Ce in the synthesis process3+As auxiliary reagent, the number of material surface Lacking oxygen, Jin Erke may be increased
The ligancy of adjacent metal catalytic site is effectively reduced, and adjusts the electronic structure of catalyst, improves the intrinsic oxygen of elctro-catalyst
Change activity.
Summary of the invention
It is an object of the present invention to it is insufficient for existing electro-catalysis analysis Oxygen Electrode Material performance, propose a kind of nickel foam
The method that stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode, with Nickelous nitrate hexahydrate
With Fe(NO3)39H2O be source of iron and nickel source, six nitric hydrate ceriums are auxiliary synthetics, urea is hydrolytic reagent, and nickel foam is conduction
Matrix, through hydro-thermal method, on nickel foam conducting base surface, the three-dimensional nickel-ferric spinel nano lamellar material of a step growth in situ,
Due to the surface coordination effect of cerium ion in the synthesis process, relatively thin nickel-ferric spinel nano lamellar material can be formed, and promote
Increase the Lacking oxygen number of material surface, causes the ligancy of catalytic active center (nickel and iron) to reduce and increase with activity.It will
The material analyses oxygen electrode as electro-catalysis, shows good, stable oxygen evolution reaction performance in 1 mol/L KOH electrolyte,
I.e. in 10 mA cm-2Overpotential under current density is only 186 mV, in 50 mA cm-2After current density, 18 h, analysis oxygen electricity
Position variation is only 0.2%.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method that nickel foam stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode, packet
Include following steps:
1) by Nickelous nitrate hexahydrate (Ni (NO3)2·6H2O), Fe(NO3)39H2O (Fe (NO3)3·9H2O), six nitric hydrate cerium
(Ce (NO3)3·6H2O) and urea, it is added in 60 ml ultrapure waters by certain molar ratio, after agitated processing, is formed pale brown
Color homogeneous mixture solotion；
2) by 1 × 2 cm2Nickel foam (NF) is immersed in the hydrochloric acid of 3 mol/L, ultrasound acidification activation 5-10 min, respectively in ethyl alcohol
After being cleaned by ultrasonic 10 min in ultrapure water, NF is immersed in the mixed solution in step 1), using hydro-thermal method, on the surface NF,
It obtains under cerium ion auxiliary, three-dimensional nickel-ferric spinel nano lamellar material (the Ce asst-NiFe LDHs/ of growth in situ
NF), in addition, collect be not attached to the surface NF, the sediment that sinks to container bottom is centrifuged, use ultrapure water and ethyl alcohol
It alternately washs, in triplicate；
3) the Ce asst-NiFe LDHs/NF that will be obtained in step 2, in ultrapure water, ultrasonic treatment removes the miscellaneous of its surface
Matter, in thermostatic drying chamber, pure Ce asst-NiFe LDHs/NF is made in 60 DEG C of 6 h of drying；
4) the Ce asst-NiFe LDHs/NF in step 3) is cut into 1 × 1 cm2As working electrode, platinized platinum is used as to electricity
Pole, mercury oxidation mercury electrode (Hg/HgO) are used as reference electrode, and 1 mol/L potassium hydroxide (KOH) solution is as electrolyte solution
(test process is passed through high-purity N2Saturation).Above section is assembled into three-electrode system, is connected to Shanghai Chen Hua 660D electrochemistry
Work station carries out the performance test of electro-catalysis oxygen evolution reaction；
5) as a comparison, in the method for the NiFe LDHs/NF of no cerium ion auxiliary synthesis, only by six hydrations in step 1)
Cerous nitrate removes, other steps are consistent with the synthetic method of Ce asst-NiFe LDHs/NF and testing procedure.
The molar ratio of Nickelous nitrate hexahydrate described in step 1), Fe(NO3)39H2O, six nitric hydrate ceriums and urea is
0.3:0.24:0.075:4。
The revolving speed of stirring described in step 1) is 600 revs/min, and the time is 30 minutes.
The reaction temperature of hydro-thermal method described in step 2 is 120 DEG C, and the reaction time is 12 h.
The revolving speed of centrifuge separation described in step 2 is 10000 revs/min, and the time is 10 minutes/time.
The time of ultrasonic treatment described in step 3) is 5 minutes, and solvent is ultrapure water.
The beneficial effects of the present invention are:
(1) the present invention provides one kind using Nickelous nitrate hexahydrate and Fe(NO3)39H2O as source of iron and nickel source, six nitric hydrate ceriums
It is hydrolytic reagent for auxiliary synthetics, urea, nickel foam is conducting base, through one step hydro thermal method, on nickel foam conducting base surface,
Growth in situ has the three-dimensional nickel-ferric spinel nano lamellar material of abundant Lacking oxygen.Its synthetic method is simple, raw material is easy to get, valence
Lattice are cheap, practical value with higher.
(2) present invention by a variety of characterization methods analyze pure NiFe LDHs/NF, Ce asst-NiFe LDHs/NF and this
Sediment in two kinds of material synthesis processes, it was demonstrated that cerium ion only conduct in the synthesis process of Ce asst-NiFe LDHs/NF
Synthetic agent is assisted, due to its Ce2+Ionic radius (1.034) is much larger than Ni2+(0.69) and Fe3+(0.645) from
Sub- radius, in the synthesis process, cerium ion are difficult in the lattice for being inserted into NiFe LDHs material.Further, since cerium ion is smaller
Electronegativity, be easy in the synthesis process with NiFe LDHs material surface oxygen be coordinated, formed alkaline carbonic acid cerium compound precipitating,
To introduce a large amount of Lacking oxygens in prepared NiFe LDHs material surface, this make low coordination metal active centres (nickel and
Iron) activity increase, greatly increase the electro-catalysis analysis oxygen ability of nickel-ferric spinel nano lamellar material.
(3) present invention due to three-dimensional assembling ultra-thin nickel-ferric spinel nanometer sheet elctro-catalyst surface have oxygen-enriched vacancy,
The Ni of high activity2+And Fe3+The advantages that metal active centres, shows excellent so that the active surface area of elctro-catalyst increases
OER activity, in 10 mA cm-2Current density under, it is only necessary to lower overpotential (186 mV), corresponding low tower phenanthrene slope is about
For 47 mV dec-1, and in 50 mA cm-2Current density under with 18 h good stability.Oxygen is analysed in its electro-catalysis
It can be better than the pure NiFe-LDHs base electrode material of most prior art.
Detailed description of the invention
Fig. 1 is the XRD spectra of pure NiFe LDHs/NF and Ce asst-NiFe LDHs/NF；
Fig. 2 is the XRD spectra of the deposit of Ce asst-NiFe LDHs；
Fig. 3 is (a) pure NiFe LDHs/NF, and (b) field emission scanning electron microscope (FESEM) of Ce asst-NiFe LDHs/NF shines
Piece；
Fig. 4 is the EDS spectrogram of Ce asst-NiFe LDHs/NF；
Fig. 5 is the transmission electron microscope (TEM) and high-resolution TEM(HRTEM of Ce asst-NiFe LDHs/NF) photo；
Fig. 6 is the Zeta potential figure of (a) NiFe LDHs/NF and Ce asst-NiFe LDHs/NF in ultrapure water, (b) Ce
The XPS full scan spectrogram of asst-NiFe LDHs/NF, the XPS fine scanning spectrogram (c) of Ce asst-NiFe LDHs/NF
O1s, (d) Ni2p, (e) Fe2p and (f) Ce3d；
Fig. 7 is (a) linear sweep voltammetry figure of NiFe LDHs/NF and Ce asst-NiFe LDHs/NF in 1 M KOH
(LSV), illustration is in 10 mA cm-2The enlarged drawing of LSV figure under current density, (b) Tafel slope figure, (c) electrochemical impedance
Scheme (EIS) and (d) the stability test figure of Ce asst-NiFe LDHs/NF.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
A kind of nickel foam stromal surface cerium ion assisted in situ modifies the side of three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode
Method, comprising the following steps:
1) by Nickelous nitrate hexahydrate (Ni (NO3)2·6H2O), Fe(NO3)39H2O (Fe (NO3)3·9H2O), six nitric hydrate cerium
(Ce (NO3)3·6H2O) and urea is with certain molar ratio 0.3:0.24:0.075:4, is added in 60 ml ultrapure waters, through 600
After rev/min 30 min of stir process, brown color homogeneous mixture solotion is formed；
2) by 1 × 2 cm2Nickel foam (NF) is immersed in the hydrochloric acid of 3 mol/L, ultrasound acidification activation 5-10 min, respectively in ethyl alcohol
After being cleaned by ultrasonic 10 min in ultrapure water, nickel foam is immersed in homogeneous solution obtained in step 1), using hydro-thermal method,
Through reacting 12 h at 120 DEG C, in foam nickel surface, obtain under cerium ion auxiliary, the three-dimensional nickel-ferric spinel of growth in situ is received
Rice flaky material (Ce asst-NiFe LDHs/NF), in addition, collecting the precipitating for being not attached to the surface NF, sinking to container bottom
Object is centrifuged through 10000 revs/min, 10 minutes/time, is alternately washed using ultrapure water and ethyl alcohol, in triplicate.
3) by Ce asst-NiFe LDHs/NF obtained in step 2,5 min are ultrasonically treated, in ultrapure water to go
Except surface impurity, in thermostatic drying chamber, pure Ce asst-NiFe LDHs/NF is made in 60 DEG C of 6 h of drying.
4) the Ce asst-NiFe LDHs/NF in step 3) is cut into 1 × 1 cm2As working electrode, platinized platinum conduct pair
Electrode, mercury oxidation mercury electrode (Hg/HgO) are used as reference electrode, and 1 mol/L potassium hydroxide (KOH) solution is as electrolyte solution
(test process is passed through high-purity N2Saturation).Above section is assembled into three-electrode system, is connected to Shanghai Chen Hua 660D electrochemistry
Work station carries out the performance test of electro-catalysis oxygen evolution reaction.
5) as a comparison, in the method for the NiFe LDHs/NF of no cerium ion auxiliary synthesis, only by six in step 1)
Nitric hydrate cerium removes, other steps are consistent with the synthetic method of Ce asst-NiFe LDHs/NF and testing procedure.
One, the characterization of pure NiFe LDHs/NF and Ce asst-NiFe LDHs/NF nanometer sheet material:
1. in order to confirm that Ce species are only used as the auxiliary reagent of NiFe LDHs system, and being not incorporated into NiFe LDHs system, use
X-ray energy spectrometer EDS analysis and XRD characterize material.
Fig. 1 be pure NiFe LDHs/NF, Ce asst-NiFe LDHs/NF XRD spectrum, 11.8 °, 23.6 ° and 34.6 °
Diffraction maximum is belonging respectively to (003) of NiFe LDHs, (006) and (009) feature crystal face.Fig. 2 is NiFe LDHs and Ce asst-
The XRD spectrum of NiFe LDHs sediment, in addition to the similar NiFe LDHs characteristic diffraction peak of Fig. 1 is presented, in Ce asst-NiFe
In the sediment of LDHs, Ce (OH) CO is detected3The XRD diffraction maximum (Fig. 2) of (JCPDS 44-0617), but in Ce asst-
The diffraction maximum (Fig. 1) of cerium-containing compound is had no in NiFe LDHs/NF.These results demonstrate, and on the surface NF, are prepared in situ
Ce asst-NiFe LDHs without cerium.
Pure NiFe LDHs/NF and Ce asst-NiFe LDHs/NF shows many vertical arrangements and interconnects as seen from Figure 3
3D assemble nanometer piece, in pure NiFe LDHs/NF the average thickness of nanometer sheet be in 44.44 nm(Fig. 3 a), and Ce asst-
The thinner thickness of NiFe LDHs/NF nanometer sheet is (in 5.74 nm, Fig. 3 b).The EDS that Fig. 4 is Ce asst-NiFe LDHs/NF is composed
Figure, as seen from the figure, Ce do not appear in the EDS spectrum of Ce asst-NiFe LDHs/NF, this result is consistent with XRD analysis.Into one
It is visible (Fig. 5) to walk microscopic analysis, layer structure and Characteristic Lattice striped (0.26 nm) is presented in Ce asst-NiFe LDHs/NF,
The latter corresponds to (012) face of NiFe LDHs structure.
2. in order to study the surface charge properties and electrocatalysis of Ce asst-NiFe LDHs/NF and NiFe LDHs/NF
Interaction between matter carries out phenetic analysis using Zeta potential and x-ray photoelectron spectroscopy (XPS).
In Fig. 6 in a, the Zeta potential (16.62 mV) on the surface Ce asst-NiFe LDHs/NF is much larger than NiFe LDHs/
NF(9.05 mV), show that the former surface is in electropositive character, this is attributable to the sky of the oxygen on the surface Ce asst-NiFe LDHs/NF
Position is increased, and leads to Ni2+And Fe3+The increase of dangling bonds and active site.B shows NiFe LDHs/NF and Ce in Fig. 6
The XPS full scan of asst-NiFe LDHs/NF measures spectrum, in O 1s spectrum (c in Fig. 6), occurs 3 in both material surfaces
Kind O substance (O1-O3), it is characterized in that: 1) the lattice surface oxygen atom (O1) in conjunction with Ni or Fe has lower combination energy
(530.1 eV), 2) Lacking oxygen or defect oxygen (O2) be medium combination can (531.3 eV), 3) surface adsorbed oxygen (O3) then has
Higher combination energy (532.7 eV).In addition, c is as it can be seen that using Ce from Fig. 63+As auxiliary reagent, can generate on the surface of the material
More Lacking oxygens (O2) reduce material Ni or the lattice surface oxygen atom (O1) of the adjacent combination of Fe, thus the low coordination in surface
Ni and Fe ion more effectively adsorb H2O is finally reached the purpose for promoting OER electro catalytic activity.Fig. 6 Ce asst- in d
The Ni 2p of NiFe LDHs/NF and NiFe LDHs/NF3/2(855 eV), Ni 2p1/2(872 eV) and corresponding power spectrum satellites
(sat.) correspond to Ni2+Oxidation state.In Fig. 6 in e both materials Fe 2p3/2(712 eV) and Fe 2p1/2(725 eV) table
It is bright to exist in Fe2+Oxidation state.Compared with pure NiFe LDHs/NF, Ni and Fe in Ce asst-NiFe LDHs/NF nanometer sheet
0.44 eV(Ni is moved in conjunction with can slightly bear) and 0.19 eV(Fe), show that the oxidation state of transition metal reduces, this is also demonstrated that
The presence of low coordinating metal.In addition, do not observe the signal of Ce substance in the Ce 3d spectrum of f in Fig. 6, this and XRD analysis knot
Fruit is consistent.
Two, electro-catalysis OER performance characterization
The a from Fig. 7 is as it can be seen that when current density is 10 mA cm-2When, the overpotential of Ce asst-NiFe LDHs/NF is only 186
MV, than NiFe LDHs/NF(208 mV) it is lower；In addition Ce asst-NiFe LDHs/NF electrode only needs that 246 mV's is excessively electric
Position, corresponding current density just can reach 200 mA cm-2, it is far below corresponding NiFe LDH/NF electrode.Further to analyze
The OER dynamic performance (b in Fig. 7) of elctro-catalyst, Ce asst-NiFe LDHs/NF(47 mV dec-1) Tafel slope
Obviously than NiFe LDHs/NF(78 mV dec-1) lower, this demonstrate that Ce asst-NiFe LDHs/NF is with superior
OER dynamic performance.The charge transfer resistance of the visible Ce asst-NiFe LDHs/NF of c is less than NiFe LDHs/NF's in Fig. 7
Charge transfer resistance shows that the former has faster electric charge transfer in electro-catalysis OER reaction process.In addition, we also test
The stability (d in Fig. 7) of Ce asst-NiFe LDHs/NF, in 50 mA cm-2After current density, 18 h test, analysis oxygen electricity
Position variation is only 0.2 %.These results indicate that nickel foam stromal surface cerium ion assisted in situ described in this patent modifies three-dimensional nickel
The method that oxygen electrode is analysed in molten iron talcum electro-catalysis, can effectively increase the Lacking oxygen quantity on surface, improve urging for surface metal
Change activity, is a kind of effective ways for improving OER performance.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (5)
1. a kind of method that nickel foam stromal surface cerium ion assisted in situ modifies three-dimensional nickel-ferric spinel electro-catalysis analysis oxygen electrode,
It is characterized by comprising following steps:
1) by Nickelous nitrate hexahydrate, Fe(NO3)39H2O, six nitric hydrate ceriums and urea, 60 are added to by certain molar ratio
In ml ultrapure water, after agitated processing, brown color homogeneous mixture solotion is formed；
2) by 1 × 2 cm2Nickel foam is immersed in the hydrochloric acid of 3 mol/L, ultrasound acidification activation 5-10 min, respectively in ethyl alcohol and super
After being cleaned by ultrasonic 10 min in pure water, nickel foam is immersed in the mixed solution in step 1), using hydro-thermal method, in nickel foam table
Face obtains under cerium ion auxiliary, the three-dimensional nickel-ferric spinel nano lamellar material Ce asst-NiFe LDHs/ of growth in situ
NF；
3) the Ce asst-NiFe LDHs/NF that will be obtained in step 2, in ultrapure water, ultrasonic treatment removes the miscellaneous of its surface
Matter, in thermostatic drying chamber, pure Ce asst-NiFe LDHs/NF is made in 60 DEG C of 6 h of drying.
2. nickel foam stromal surface cerium ion assisted in situ according to claim 1 modifies three-dimensional nickel-ferric spinel electro-catalysis
The method for analysing oxygen electrode, it is characterised in that: Nickelous nitrate hexahydrate described in step 1), Fe(NO3)39H2O, six nitric hydrates
The molar ratio of cerium and urea is 0.3:0.24:0.075:4.
3. nickel foam stromal surface cerium ion assisted in situ according to claim 1 modifies three-dimensional nickel-ferric spinel electro-catalysis
The method for analysing oxygen electrode, it is characterised in that: the revolving speed of stirring described in step 1) is 600 revs/min, and the time is 30 minutes.
4. nickel foam stromal surface cerium ion assisted in situ according to claim 1 is modified three-dimensional nickel-ferric spinel electricity and is urged
Change the method for analysis oxygen electrode, it is characterised in that: the reaction temperature of hydro-thermal method described in step 2 is 120 DEG C, the reaction time 12
h。
5. nickel foam stromal surface cerium ion assisted in situ according to claim 1 modifies three-dimensional nickel-ferric spinel electro-catalysis
The method for analysing oxygen electrode, it is characterised in that: the time of ultrasonic treatment described in step 3) is 5 minutes.
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