CN109811360A - A kind of NiFeMo ternary electrolysis water electrode and preparation method thereof - Google Patents
A kind of NiFeMo ternary electrolysis water electrode and preparation method thereof Download PDFInfo
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- CN109811360A CN109811360A CN201910183487.4A CN201910183487A CN109811360A CN 109811360 A CN109811360 A CN 109811360A CN 201910183487 A CN201910183487 A CN 201910183487A CN 109811360 A CN109811360 A CN 109811360A
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Abstract
The invention discloses a kind of NiFeMo ternary electrolysis water electrodes and preparation method thereof, first with molysite, nickel salt, urea and NH under a low-temperature hydrothermal4F is that raw material prepares NiFe-LDH/NF, then carries out low-temperature hydrothermal again with NiFe-LDH/NF and molybdate compound and obtains Ni-Fetrace@NFM/NF, then by Ni-Fetrace@NFM/NF, which is placed in the reducing atmosphere of flowing, is heat-treated certain time, obtains final material Ni/NiFeMoOx/ NF, this process LDH substrate are reduced into Ni nano particle, while the NiFe-MoO generated with the molybdate being reducedxIt is cross-linked to form the composite material with classifying porous nanometer chip architecture mutually.Classifying porous nanometer chip architecture is conducive to bubble diffusion, the alloy and MoO of formationxIt is crosslinked and there is good electric conductivity in conjunction with conductive substrates, this all makes material have excellent kinetics；The NiFe-MoO of high hydrogen evolution activityxAssigning material simultaneously with the active Ni nano particle of high oxygen separated, there is brilliant liberation of hydrogen to analyse oxygen performance, and then obtain the performance with the full electrolysis water of catalysis of application prospect.
Description
Technical field
The present invention relates to a kind of electrolysis water electrodes and preparation method thereof, and in particular to a kind of NiFeMo ternary electrolysis water electrode
And preparation method thereof.
Background technique
The increasingly depleted and caused environmental degradation problem of fossil energy makes the mankind, and there is an urgent need to seek new energy generation
It.Hydrogen Energy is one of the energy of most development potentiality, using various informative and environmentally friendly, therefore is that current various countries are competitively ground
The hot spot or even Long-term planning studied carefully.The primary premise that hydrogen is hydrogen utilization is prepared, but the main source of hydrogen is still at present
Fossil fuel, therefore develop reproducible hydrogen manufacturing mode and be of great significance.Water electrolysis hydrogen production has high conversion efficiency, technique
Simply, the high plurality of advantages of hydrogen purity is made is considered as a kind of ideal hydrogen manufacturing method.Water electrolysis hydrogen production can acid or
It is carried out in alkaline electrolyte.It needs under acid condition using precious metals pt and IrO2/RuO2As catalyst, but noble metal is limited
Reserves and fancy price carry out electrolysis water under acid condition can not on a large scale.Electrolysis water master under alkaline condition at present
It to use metallic nickel and stainless steel as electrode, but due to the presence of overpotential high in electrolytic process, lead to capacity usage ratio
Low, economic benefit is undesirable.Therefore, the base metal liberation of hydrogen oxygen-separating catalyst for developing lower price high efficiency has become electrolysis water
The key point of scale application.
Transition metal analyses oxygen catalytic performance with excellent liberation of hydrogen because its electronic structure and noble metal are close.But mesh
Often performance can not match in excellence or beauty the transition-metal catalyst of preceding preparation with noble metal, in addition, most of catalyst only have liberation of hydrogen or analysis
The single catalytic performance performance of oxygen is outstanding, and whole electro-catalysis hydrolysis property has still combined larger gap with noble metal.Therefore,
It develops a kind of while having the two-functional electrolytic catalyst of excellent liberation of hydrogen analysis oxygen performance significant.Long-term research table
Bright nickel base nanometer material has excellent analysis oxygen (OER) catalytic performance, but its liberation of hydrogen (HER) performance is undesirable.It is newest simultaneously
Research shows that Ni-Mo-O compound (Nature Communications 2017,15437.Advanced Materials
2017,1703311) nano material has the Hydrogen Evolution Performance for the Pt that matches in excellence or beauty, but it analyses oxygen degraded performance.And develop in combination with
The two-functional electrolytic material of the high liberation of hydrogen oxygen evolution activity of two class materials is still a challenge.
Catalysis material, which is grown directly upon in three-dimensional conductive substrate, can increase substantially material conductivity, while be conducive to gas
The quick diffusion of bubble, this is conducive to the catalytic performance for improving material.In addition, material, which is cross-linked with each other, generates layered multi-stage nanometer sheet
Structure is conducive to the active site exposure for further making material while improving material conductivity.
Summary of the invention
According to the above-mentioned deficiencies of the prior art, the present invention provides a kind of NiFeMo ternary electrolysis water electrode and its preparation side
Method has the double catalysis of liberation of hydrogen analysis oxygen, and has the characteristics that Cheap highly effective, base metal at low cost.
A kind of NiFeMo ternary electrolysis water electrode of the present invention, it is characterised in that: the NiFeMo ternary electrolysis water
Electrode is NiFe-MoOxIt is cross-linked to form receiving with graded porous structure mutually in conjunction with the compound and the two of Ni nano particle
Rice piece is simultaneously grown on three-dimensional conductive base foam nickel, wherein the NiFe-MoOxFor the non-whole of unbodied NiFe doping
Compare MoOx。
A kind of preparation method of NiFeMo ternary electrolysis water electrode of the present invention, specific preparation process is as follows:
(1) by molysite, nickel salt, NH4F and urea are dissolved in deionized water, and nickel foam is added after being completely dissolved and carries out
Hydro-thermal is cleaned after cooling and obtains foamed nickel supported NiFe double-metal hydroxide, i.e. NiFe-LDH/NF；
(2) molybdate compound is dissolved in deionized water, then NiFe-LDH/NF is put into and is carried out hydro-thermal, after cooling
It is cleaned to obtain Ni-Fetrace@NFM/NF；
(3) Ni-Fe for obtaining step (2)trace@NFM/NF, which is placed in the reducing atmosphere of flowing, to be heat-treated, finally
Obtain Ni/NiFeMoOx/NF。
Wherein, preferred embodiment is as follows:
Molysite substance withdrawl syndrome is 5mmol/L~20mmol/L, the molysite and nickel salt substance in the step (1)
Amount concentration ratio be 1:1~20, the urea substance withdrawl syndrome be 100~400mmol/L, the amount of the ammonium fluoride substance
Concentration is 30~300mmol/L, and the molysite is one of ferric nitrate, iron chloride or ferric sulfate, and the nickel salt is nitre
One of sour nickel, nickel acetate, nickel chloride or nickel sulfate.
The time of hydro-thermal is 2h~48h in the step (1), and hydrothermal temperature is 100 DEG C~200 DEG C.
Nickel foam and deionized water quality ratio are 1:10~1:400 in the step (1).
Molybdate compound substance withdrawl syndrome is 5mmol/L~40mmol/L, the molybdate compound in the step (2)
For one of ammonium heptamolybdate, ammonium molybdate or sodium molybdate.
The time of hydro-thermal is 2h~36h in the step (2), and hydrothermal temperature is 100 DEG C~200 DEG C.
Reducing atmosphere is one of hydrogen or carbon monoxide in the step (3), when using hydrogen as reducing atmosphere,
Also need to be passed through argon gas as protection gas, the usually ratio of the two is 5%VH2/ 95%VAr。
The condition being heat-treated in the step (3) is that 1h~for 24 hours is heat-treated at 300 DEG C~800 DEG C.
The preparation method is that first with molysite, nickel salt, urea and NH under a low-temperature hydrothermal4F is raw material system
Standby NiFe-LDH/NF out, is then carried out low-temperature hydrothermal with NiFe-LDH/NF and molybdate compound again and obtains Ni-Fetrace@NFM/
NF, then by Ni-Fetrace@NFM/NF, which is placed in the reducing atmosphere of flowing, is heat-treated certain time, obtain final material Ni/
NiFeMoOx/ NF, this process LDH substrate are reduced into Ni nano particle, while the NiFe-MoO generated with the molybdate being reducedx
It is cross-linked to form the composite material with classifying porous nanometer chip architecture mutually.Classifying porous nanometer chip architecture spreads conducive to bubble,
The alloy and MoO of formationxIt is crosslinked and there is good electric conductivity in conjunction with conductive substrates, it is excellent that this has material
Kinetics；The NiFe-MoO of high hydrogen evolution activityxAssigning material simultaneously with the active Ni nano particle of high oxygen separated has brilliance
Liberation of hydrogen analyse oxygen performance, and then obtain the performance with the full electrolysis water of catalysis of application prospect.
The present invention has the advantage that
1) metal salt according to the present invention, urea, NH4F, solvent and reducing atmosphere are cheap and easy to get, preparation cost
It is low；
2) the step of present invention is carried out (1) and step (2) hydrothermal temperature is lower, and scale application prospect is preferable；
3) all material treatment process of the present invention is simple, is not related to making for strong corrosive, strong oxidizing property and extremely toxic substance
With feasibility is high；
4) NiFeMo ternary electrolysis water electrode prepared by the present invention is by the NiFe-MoO of high hydrogen evolution activityxWith high oxygen separated activity
Ni nano particle be combined together, solve for a long time a kind of material only have relatively a kind of predicament of good catalytic performance.
Compound, the porous structure of high active substance and good electric conductivity make Ni/NiFeMoOx/ NF obtains excellent liberation of hydrogen
Analyse oxygen and good electrolysis water catalytic performance.
Detailed description of the invention
Fig. 1 (a) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe SEM of/NF schemes；
Fig. 1 (b) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe TEM of/NF schemes；
Fig. 1 (c) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe HRTEM of/NF schemes, and inserts
Figure is selective electron diffraction figure；
Fig. 1 (d) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe mercury injection method aperture of/NF point
Butut；
Fig. 1 (e) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe BET test chart of/NF,
Illustration is corresponding graph of pore diameter distribution；
Fig. 1 (f) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe XRD x ray diffraction of/NF
Datagram；
Fig. 2 (a) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe Mo 3d XPS of/NF schemes；
Fig. 2 (b) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe O 1sXPS of/NF schemes；
Fig. 2 (c) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe EXAFS of/NF schemes；
Fig. 2 (d) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe XANES of/NF schemes；
Fig. 2 (e1) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 3 obtainsxThe SEM of/NF schemes；
Fig. 2 (e2) is the EDS figure schemed in the rectangular area (e1)；
Fig. 3 (a) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 4 obtainsx/ NF is in 1M potassium hydroxide
The HER polarization curve of electrochemical property test in aqueous solution；
Fig. 3 (b) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 4 obtainsx/ NF is in 1M potassium hydroxide
The HER stability test figure of electrochemical property test in aqueous solution；
Fig. 3 (c) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 4 obtainsx/ NF is in 1M potassium hydroxide
The OER polarization curve of electrochemical property test in aqueous solution；
Fig. 3 (d) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 4 obtainsx/ NF is in 1M potassium hydroxide
The OER steady testing figure of electrochemical property test in aqueous solution；
Fig. 3 (e) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 4 obtainsxElectrolysis water is helped in/NF assembling
When device, in technical grade 500mA/cm2Continuous work is more than 200 hours test charts under high current density；
Fig. 4 (a) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 11 obtainsx/ NF is in 1M potassium hydroxide
In aqueous solution full electrolysis water for 24 hours after HER electrode SEM figure I；
Fig. 4 (b) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 11 obtainsx/ NF is in 1M potassium hydroxide
In aqueous solution full electrolysis water for 24 hours after HER electrode SEM figure II；
Fig. 4 (c) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 11 obtainsx/ NF is in 1M potassium hydroxide
In aqueous solution full electrolysis water for 24 hours after OER electrode SEM figure I；
Fig. 4 (d) is the NiFeMo ternary electrolysis water electrode Ni/NiFeMoO that embodiment 11 obtainsx/ NF is in 1M potassium hydroxide
In aqueous solution full electrolysis water for 24 hours after OER electrode SEM figure II.
Specific embodiment
The present invention will be further described with attached drawing with reference to embodiments.
Embodiment 1:
Weigh 0.24g urea, 0.05g ammonium fluoride, 0.4mmol Fe(NO3)39H2O, 8mmol Nickelous nitrate hexahydrate is dissolved in
The bubble that a piece of 2g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in 40ml deionized water, after stirring and dissolving
Foam nickel, 100 DEG C of hydro-thermal 2h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material,
It is put into the ammonium heptamolybdate aqueous solution that 40ml substance withdrawl syndrome is 20mmol/L, is transferred to 120 DEG C of hydro-thermals in 50ml reaction kettle
10h.After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube,
Carbon monoxide atmosphere is maintained, 350 DEG C is warming up to 5 DEG C/min rate and keeps 2h, material is changed into black by brick-red, both
Obtain NiFeMo ternary electrolysis water electrode.
Embodiment 2:
Weigh 0.6g urea, 0.2g ammonium fluoride, 8mmol Fe(NO3)39H2O, 8mmol Nickelous nitrate hexahydrate is dissolved in 40ml and goes
The nickel foam that a piece of 0.1g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in ionized water, after stirring and dissolving,
100 DEG C of hydro-thermal 20h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, be put into
40ml substance withdrawl syndrome is to be transferred to 150 DEG C of hydro-thermal 20h in 50ml reaction kettle in the ammonium heptamolybdate aqueous solution of 40mmol/L.
After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube, maintain
5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, be warming up to 300 DEG C with 5 DEG C/min rate and keep 10h, material by
It is brick-red to be changed into black, both obtain NiFeMo ternary electrolysis water electrode.
Embodiment 3:
Weigh 0.6g urea, 0.2g ammonium fluoride, 0.4mmol Fe(NO3)39H2O, 5mmol Nickelous nitrate hexahydrate is dissolved in 40ml
The foam that a piece of 0.6g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in deionized water, after stirring and dissolving
Nickel, 120 DEG C of hydro-thermal 12h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material,
It is put into the ammonium heptamolybdate aqueous solution that 40ml substance withdrawl syndrome is 10mmol/L, is transferred to 120 DEG C of hydro-thermals in 50ml reaction kettle
10h.After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube,
Maintain 5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, 400 DEG C are warming up to 5 DEG C/min rate and keep 2h, material
It is changed into black by brick-red, both obtains NiFeMo ternary electrolysis water electrode.
By Fig. 1 (a) it can be seen that material is aligned in the nanometer chip architecture in nickel foam, Fig. 1 (b) is it can be seen that material
With porous structure, Fig. 1 (d) and Fig. 1 (e) are it can be seen that the layering porous structure that material has micrometer-submicrometer-mesoporous, figure
1 (f) it can be seen that there is the phase of W metal in material, and other positions show that there are amorphous knots in material without obvious appearance
Structure, this is corresponding with the selection electronic diffraction result in the lattice and Fig. 1 (c) illustration of Fig. 1 (c) Ni (111) crystal face occurred.
By the Mo in material known to Fig. 2 (a) with Mo6+And Mo5+Form exists, there are Lacking oxygen in Fig. 2 (b) material,
Occurs apparent similar MoO in Fig. 2 (c)3Mo-O ABSORPTION EDGE, while there is the total hexahedral ABSORPTION EDGE of side Mo-Mo,
Illustrate Mo with Lacking oxygen non-stoichiometric MoOxIn the presence of wherein MoOxOctahedral structure, Fig. 2 are formed in such a way that Mo-Mo key is total to side
(d) disappearance of side leading peak illustrates the change of material crystalline structure at material 22008eV in, while ABSORPTION EDGE is compared to Ni-Fe
The Forward of LDH@NFM also turns out that the Mo element of material is reduced and valence state reduces.Fig. 2 (e1-e2) and table 1 know the group of material
Element is mainly Ni, Mo, O, in addition, having a small amount of Fe doping in the material.
Each element content table in the rectangular area table 1: Fig. 2 (e1)
| Elt | Line | Atomic% | Conc | Units | |
| C | Ka | 19.789 | 6.020 | Wt.% | |
| O | Ka | 35.896 | 14.546 | Wt.% | |
| Fe | Ka | 1.273 | 1.800 | Wt.% | |
| Ni | Ka | 28.586 | 42.507 | Wt.% | |
| Mo | La | 14.456 | 35.127 | Wt.% | |
| 100.000 | 100.000 | Wt.% | Total |
To sum up material prepared known to all charts is the amorphous NiFe doping being arranged on nickel screen with oxygen
The lower valency MoO in vacancyxIn conjunction with the molecular porous nano chip arrays of Ni nanoparticle.
Embodiment 4:
Weigh 0.6g urea, 0.2g ammonium fluoride, 0.4mmol Fe(NO3)39H2O, 4mmol Nickelous nitrate hexahydrate is dissolved in 40ml
The foam that a piece of 0.6g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in deionized water, after stirring and dissolving
Nickel, 120 DEG C of hydro-thermal 12h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material,
It is put into the ammonium heptamolybdate aqueous solution that 40ml substance withdrawl syndrome is 40mmol/L, is transferred to 150 DEG C of hydro-thermals in 50ml reaction kettle
15h.After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube,
Maintain 5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, 400 DEG C are warming up to 5 DEG C/min rate and keep 2h, material
It is changed into black by brick-red, both obtains NiFeMo ternary electrolysis water electrode.
Fig. 3 (a) and Fig. 3 (b) is HER polarization curve and stability test figure respectively, and catalytic performance is expensive close to being commercialized
Metallic catalyst Pt/C, while energy is had excellent stability, property retention is constant after 1000 coils circulations, in -0.045V
Current density does not decline the work of (vs RHE) constant potential for 24 hours.Fig. 3 (c) and Fig. 3 (d) is OER polarization curve and stabilization respectively
Property test chart, catalytic performance far superior to be commercialized noble metal catalyst IrO2, while energy is had excellent stability,
Property retention is constant after 1000 coils circulations, and in the work of 1.557V (vs RHE) constant potential, current density does not decline for 24 hours.
When electrode assembling is helped electrolytic water device by Fig. 3 (e) display, in technical grade 500mA/cm2Continuous work is super under high current density
It crosses 200 hours voltage to be held essentially constant, shows good industrial applications prospect.
Embodiment 5:
Weigh 0.96g urea, 0.4g ammonium fluoride, 4mmol Fe(NO3)39H2O, 8mmol Nickelous nitrate hexahydrate is dissolved in 40ml
The foam that a piece of 0.6g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in deionized water, after stirring and dissolving
Nickel, 160 DEG C of hydro-thermals of baking oven are for 24 hours.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material,
It is put into the ammonium heptamolybdate aqueous solution that 40ml substance withdrawl syndrome is 5mmol/L, is transferred to 200 DEG C of hydro-thermals in 50ml reaction kettle
3h.After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube,
Carbon monoxide atmosphere is maintained, 500 DEG C is warming up to 5 DEG C/min rate and keeps 1h, material is changed into black by brick-red, both
Obtain NiFeMo ternary electrolysis water electrode.
Embodiment 6:
Weigh 0.5g urea, 0.3g ammonium fluoride, 0.8mmol Fe(NO3)39H2O, 8mmol Nickelous nitrate hexahydrate is dissolved in 80ml
The foam that a piece of 0.8g was cleaned with 3mol hydrochloric acid is transferred in 100ml reaction kettle and is added in deionized water, after stirring and dissolving
Nickel, 200 DEG C of hydro-thermal 48h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, put
Enter in the ammonium heptamolybdate aqueous solution that 80ml substance withdrawl syndrome is 40mmol/L, is transferred to 100 DEG C of hydro-thermals in 100ml reaction kettle
36h.After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube,
Maintain 5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, 700 DEG C are warming up to 5 DEG C/min rate and keep 10h, material
Material is changed into black by brick-red, both obtains NiFeMo ternary electrolysis water electrode.
Embodiment 7:
Weigh 0.4g urea, 0.1g ammonium fluoride, 1mmol ferric chloride hexahydrate, 8mmol six hydration nickel sulfate is dissolved in 40ml and goes
The nickel foam that a piece of 0.6g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in ionized water, after stirring and dissolving,
180 DEG C of hydro-thermal 5h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, be put into
40ml substance withdrawl syndrome is to be transferred to 120 DEG C of hydro-thermal 10h in 50ml reaction kettle in the sodium molybdate aqueous solution of 40mmol/L.Knot
It is cleaned after beam and obtains the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube, maintained
5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, with 5 DEG C/min rate be warming up to 400 DEG C and keep for 24 hours, material by
It is brick-red to be changed into black, both obtain NiFeMo ternary electrolysis water electrode.
Embodiment 8:
Weigh 0.6g urea, 0.2g ammonium fluoride, 2mmol ferric chloride hexahydrate, 2mmol Nickel dichloride hexahydrate is dissolved in 40ml and goes
The nickel foam that a piece of 0.6g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in ionized water, after stirring and dissolving,
120 DEG C of hydro-thermals of baking oven are for 24 hours.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, be put into
40ml substance withdrawl syndrome is to be transferred to 150 DEG C of hydro-thermal 10h in 50ml reaction kettle in the ammonium heptamolybdate aqueous solution of 25mmol/L.
After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube, maintain
5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, be warming up to 400 DEG C with 5 DEG C/min rate and keep 15h, material by
It is brick-red to be changed into black, both obtain NiFeMo ternary electrolysis water electrode.
Embodiment 9:
Weigh 0.6g urea, 0.2g ammonium fluoride, 1mmol sulfuric acid monohydrate iron, 10mmol nickel acetate tetrahydrate is dissolved in 40ml
The nickel foam that a piece of 1g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in deionized water, after stirring and dissolving,
100 DEG C of hydro-thermal 40h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, be put into
40ml substance withdrawl syndrome is to be transferred to 180 DEG C of hydro-thermal 20h in 50ml reaction kettle in the sodium molybdate aqueous solution of 40mmol/L.Knot
It is cleaned after beam and obtains the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube, maintain one
Carbonoxide atmosphere is warming up to 800 DEG C with 5 DEG C/min rate and keeps 3h, and material is changed into black by brick-red, both obtains NiFeMo
Ternary electrolysis water electrode.
Embodiment 10:
Weigh 0.6g urea, 0.2g ammonium fluoride, 0.4mmol ferric chloride hexahydrate, 8mmol Nickel dichloride hexahydrate is dissolved in 40ml
The nickel foam that a piece of 1g was cleaned with 3mol hydrochloric acid is transferred in 50ml reaction kettle and is added in deionized water, after stirring and dissolving,
120 DEG C of hydro-thermal 12h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material foam nickel material, be put into
40ml substance withdrawl syndrome is to be transferred to 160 DEG C of hydro-thermal 10h in 50ml reaction kettle in the ammonium heptamolybdate aqueous solution of 40mmol/L.
After clean obtain the foam nickel material that surface covers brick-red material, be put into after drying in tube furnace Quartz stove tube, maintain
5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, 600 DEG C are warming up to 5 DEG C/min rate and keeps 2h, and material is by brick
Red is changed into black, both obtains NiFeMo ternary electrolysis water electrode.
Embodiment 11:
Weigh 0.6g urea, 0.2g ammonium fluoride, 0.4mmol Fe(NO3)39H2O, 4.5mmol Nickelous nitrate hexahydrate is dissolved in
It is transferred in 40ml deionized water, after stirring and dissolving in 50ml reaction kettle and is added what a piece of 0.6g was cleaned with 3mol hydrochloric acid
Nickel foam, 120 DEG C of hydro-thermal 12h of baking oven.After take out nickel foam clean obtain surface covering yellow-green material nickel foam material
Material is put into the ammonium molybdate aqueous solution that 40ml substance withdrawl syndrome is 40mmol/L, is transferred to 120 DEG C of water in 50ml reaction kettle
Hot 10h.After clean obtain the foam nickel material that surface covers brick-red material, tube furnace Quartz stove tube is put into after drying
In, maintain 5% (5%VH2/ 95%VAr) hydrogen argon gas mixed atmosphere, 400 DEG C are warming up to 5 DEG C/min rate and keep 2h,
Material is changed into black by brick-red, both obtains NiFeMo ternary electrolysis water electrode.
As shown in Fig. 4 (a)~Fig. 4 (d), electron microscope illustrate material prolonged electrolysis water test after, whole pattern knot
Arriving for structure is kept, and shows excellent structural stability.
Claims (9)
1. a kind of NiFeMo ternary electrolysis water electrode, it is characterised in that: the NiFeMo ternary electrolytic water electric extremely NiFe-MoOx
Compound and the two in conjunction with Ni nano particle are cross-linked to form mutually the nanometer sheet with graded porous structure and are grown on three-dimensional
In conductive substrates nickel foam, wherein the NiFe-MoOxFor the non-stoichiometric MoO of unbodied NiFe dopingx。
2. a kind of a kind of preparation method of NiFeMo ternary electrolysis water electrode described in claim 1, it is characterised in that specific system
It is standby that steps are as follows:
(1) by molysite, nickel salt, NH4F and urea are dissolved in deionized water, and nickel foam is added after being completely dissolved and carries out hydro-thermal,
It is cleaned after cooling and obtains foamed nickel supported NiFe double-metal hydroxide, i.e. NiFe-LDH/NF；
(2) molybdate compound is dissolved in deionized water, then NiFe-LDH/NF is put into and is carried out hydro-thermal, carried out after cooling
It cleans and obtains Ni-Fetrace@NFM/NF；
(3) Ni-Fe for obtaining step (2)trace@NFM/NF, which is placed in the reducing atmosphere of flowing, to be heat-treated, and is finally obtained
Ni/NiFeMoOx/NF。
3. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly molysite substance withdrawl syndrome is 5mmol/L~20mmol/L in (1), and the molysite and nickel salt substance withdrawl syndrome ratio are 1:
1~20, the urea substance withdrawl syndrome be 100~400mmol/L, the ammonium fluoride substance withdrawl syndrome be 30~
300mmol/L, the molysite are one of ferric nitrate, iron chloride or ferric sulfate, and the nickel salt is nickel nitrate, acetic acid
One of nickel, nickel chloride or nickel sulfate.
4. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly the time of hydro-thermal is 2h~48h in (1), and hydrothermal temperature is 100 DEG C~200 DEG C.
5. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly nickel foam and deionized water quality ratio are 1:10~1:400 in (1).
6. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly molybdate compound substance withdrawl syndrome is 5mmol/L~40mmol/L in (2), and the molybdate compound is ammonium heptamolybdate, molybdenum
One of sour ammonium or sodium molybdate.
7. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly the time of hydro-thermal is 2h~36h in (2), and hydrothermal temperature is 100 DEG C~200 DEG C.
8. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly reducing atmosphere is one of hydrogen or carbon monoxide in (3).
9. a kind of preparation method of NiFeMo ternary electrolysis water electrode according to claim 2, it is characterised in that: the step
Suddenly the condition being heat-treated in (3) is that 1h~for 24 hours is heat-treated at 300 DEG C~800 DEG C.
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| CN108754532A (en) * | 2018-05-29 | 2018-11-06 | 武汉工程大学 | A kind of iron of molybdenum doping/nickel layer shape array@nickel foam based combined electrode materials and the preparation method and application thereof |
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