CN110512233A - A kind of porous carbide hydrogen-precipitating electrode and one one-step preparation method with honeycomb microstructure - Google Patents
A kind of porous carbide hydrogen-precipitating electrode and one one-step preparation method with honeycomb microstructure Download PDFInfo
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- CN110512233A CN110512233A CN201910908633.5A CN201910908633A CN110512233A CN 110512233 A CN110512233 A CN 110512233A CN 201910908633 A CN201910908633 A CN 201910908633A CN 110512233 A CN110512233 A CN 110512233A
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Abstract
The invention discloses a kind of porous carbide hydrogen-precipitating electrode and one one-step preparation method with honeycomb microstructure, the porous carbide hydrogen-precipitating electrode includes can carburizing type metallic substrates and the porous carbide coating with honeycomb microstructure.It is described can carburizing type metal include W, Mo, Ti and its alloy, or the metal or alloy containing W, Mo, Ti and its alloy coat.Preparation method are as follows: in the molten salt electrolyte containing fused carbonate, the porous silicon carbide nitride layer with honeycomb microstructure is prepared in base metal surfaces by way of catholyte carburizing.The preparation method of the electrode eliminates conductive agent and binder used in traditional liberation of hydrogen catalyst electrode, reduces material cost, reduces the complexity of hydrogen-precipitating electrode preparation.Prepared electrode has good hydrophily, and the contact angular region with water is 10 °~50 °, all has preferable liberation of hydrogen effect and liberation of hydrogen stability in acid and alkaline environment, and have wide application prospect.
Description
Technical field
The present invention relates to electrochemical technology field more particularly to a kind of porous carbide analysis with honeycomb microstructure
Hydrogen electrode and one one-step preparation method.
Background technique
With the aggravation of problem of environmental pollution caused by the exhaustion of fossil fuel and a large amount of uses of fossil fuel, environment friend
The exploitation of good type new energy has become today's society one of ten big problems urgently to be resolved.In numerous new energies, hydrogen
Have higher fuel value, and product is water after burning, avoids the generation of pollutant, is a kind of extremely promising renewable clear
The clean energy.Water electrolysis hydrogen production is considered most clean production hydrogen mode, and its production hydrogen purity is higher, but due to industrial at present
The nickel-base alloy hydrogen-precipitating electrode overpotential of hydrogen evolution of application is higher, and production hydrogen energy consumption is larger, seriously hinders current electrolysis water system
The development of standby hydrogen.
There is transition metal carbide d similar with platinum group metal to charge minor structure, accordingly show the electro-catalysis of eka-platinium
Property, thus often have been investigated as liberation of hydrogen catalyst.Current transition metal carbide liberation of hydrogen catalyst is mainly with powdered
It is main.Powdered transition metal carbide is mixed with conductive agent and binder usually, is then fixed in conductive substrates, analysis is used as
Hydrogen electrode.The electrode, which is used as hydrogen-precipitating electrode, some deficiencies: (1) addition of conductive agent and binder be easy to cause catalyst activity
The covering in site causes the reduction of hydrogen-precipitating electrode catalytic activity；(2) wetability of hydrogen-precipitating electrode in the electrolytic solution can be because of conductive agent
Addition with binder is deteriorated, and Surface Creation bubble is difficult to separate in time；(3) biggish current density condition in the industrial production
Under, powder catalyst is easy to appear obscission during liberation of hydrogen on hydrogen-precipitating electrode, reduces hydrogen-precipitating electrode stability；
(4) addition of conductive agent and binder increases material cost and process complexity in production process.Therefore, one kind is developed
The hydrogen-precipitating electrode that preparation method is simple, Hydrogen Evolution Performance is good, stability is high very it is necessary to.
Also occur that catalyst being carried on hydrogen-precipitating electrode by the method for load now, but mostly with noble metal, alloy
Based on, at high cost, preparation method is complicated, and the hydrogen-precipitating electrode having only is applicable in alkaline medium or acid medium, cannot
High efficiency is kept in all media.Such as Chinese invention patent (application number: 201811602107.8 applyings date: 2018-12-
26) disclose the preparation method of compound hydrogen-precipitating electrode of porous Ni-base copper rhenium a kind of, Chinese invention patent (application number:
201310355681.9 the applying date: 2013-08-15) disclose a kind of preparation of compound hydrogen-precipitating electrode of porous Ni-base ru oxide
Method, Chinese invention patent (application number: 201611121400.3 applyings date: 2016-12-08) disclose a kind of ordered mesopore carbon
Load nanometer iridium base electrocatalytic hydrogen evolution electrode and its preparation and application etc..
Summary of the invention
Based on the above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of micro- with honeycomb
The porous carbide hydrogen-precipitating electrode and one one-step preparation method of structure are seen, the hydrogen-precipitating electrode overpotential of hydrogen evolution is low, liberation of hydrogen stability is high,
Can the stable use for a long time in full pH electrolyte, and preparation method is easy to operate, environmentally protective, is advantageously implemented extensive life
It produces.
In order to solve the above technical problem, the present invention provides a kind of porous carbide liberation of hydrogen with honeycomb microstructure
Electrode, including can carburizing type metallic substrates and porous carbide coating with honeycomb microstructure, the porous carbide
Coating layer thickness is 0.01 μm~200 μm, and porous carbide coating aperture is 5nm~500nm.
As a preferred embodiment of the above technical solution, the porous carbide liberation of hydrogen provided by the invention with honeycomb microstructure
Electrode further comprises some or all of following technical characteristic:
As an improvement of the above technical solution, the porous carbide coating layer thickness is 11 μm~50 μm, is further 11 μ
M~50 μm, porous carbide coating aperture are 12nm~80nm.As an improvement of the above technical solution, described can carburizing
Type metal includes W, Mo, Ti and its alloy, or the metal or alloy containing W, Mo, Ti and its alloy coat.
As an improvement of the above technical solution, the carbide coating is metal-carbide coating, the metal carbides
Coating group becomes MC and/or M2C, M refer to the combination of W, Mo, Ti single metallic elements or any multiple element.
As an improvement of the above technical solution, the hydrogen-precipitating electrode has good hydrophily, and the contact angle with water is 10o
~50o.
As an improvement of the above technical solution, the shape of the metallic substrates include particle, sheet, rodlike, plate and
Cellular.
One one-step preparation method of the present invention also provides a kind of porous carbide hydrogen-precipitating electrode with honeycomb microstructure, packet
Include following steps: using fuse salt as electrolyte, using can carburizing type metal as cathode, with graphite electrode or inertia analysis oxygen electrode be
Anode applies voltage or current electroanalysis；Take out cathode after electrolysis, cleaning remove residual fuse salt obtain it is microcosmic containing honeycomb
The porous carbide hydrogen-precipitating electrode of structure.
As an improvement of the above technical solution, the molten salt electrolyte is carbonate or the melting containing carbonate
Salt；Preferably NaF-KF-Na2CO3、K2CO3-Li2CO3、CaCl2-Ca2CO3。
As an improvement of the above technical solution, working metal electrode passes through 300#, 600# carbon respectively before molten-salt electrolysis
Then the metal of grinding process is cleaned by ultrasonic 20min by dehydrated alcohol, acetone and deionized water by the polishing of SiClx sand paper.
As an improvement of the above technical solution, the electrolysis mode be potentiostatic electrolysis or constant current electrolysis or
Person's perseverance slot piezoelectricity solution；Permanent slot pressure decomposition voltage is 0.1V~3.0V；Constant-current electrolysis current density is 0.1mA cm-2~
500mA cm-2；Potentiostatic deposition current potential is -1.0V~-2.5V, reference electrode Ag/Ag2SO4；Electrolysis temperature be 450 DEG C~
900 DEG C, electrolysis time is 0.1h~6h.
As an improvement of the above technical solution, the one of the porous carbide hydrogen-precipitating electrode with honeycomb microstructure
One-step preparation method, concrete operations are as follows:
S1. the metal surface of electrolysis is polished by 300#, 600# carborundum paper, then passes through dehydrated alcohol, third
Ketone, deionized water ultrasonic cleaning, remove surface irregularities, and drying is stand-by；
S2. by the salt after 200 DEG C~300 DEG C vacuum drying treatments risen under inert atmosphere protection target temperature (450~
900℃)；
S3. step S1 treated cathode, anode are respectively put into electrolytic cell, pass through potentiostatic electrolysis or constant voltage
Electrolysis method or constant current electrolysis carry out Time constant electrolysis；
S4. after being electrolysed, after working electrode proposition fused salt liquid level is put into deionized water ultrasonic cleaning after cooling
It takes out, obtains the above-mentioned porous carbide hydrogen-precipitating electrode with honeycomb microstructure.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
This method is easy to operate, environmentally protective, is advantageously implemented large-scale production.
1. carbide hydrogen-precipitating electrode prepared by the present invention has a large amount of cellular porous microstructure, this shape characteristic
Mainly have following two points advantage: 1) honeycomb pattern, which reduces, generates bubble to the screen effect of electrode in electrolytic process；2) coarse
Honeycomb pattern increase effective electrochemical surface area of hydrogen-precipitating electrode, it is possible to provide more active sites, favorably
In the efficient production of hydrogen.
2. carbide hydrogen-precipitating electrode prepared by the present invention have good hydrophily, the contact angle with water be about 10o~
50o, contact angle test such as Fig. 3.The process that the wetability of electrode material surface prepares hydrogen for electrolysis water is very crucial, catalysis
The good wetability of agent electrode surface is not only advantageous to guarantee the best solid-liquid humidified atmosphere that elctro-catalyst is had an effect, and also has
Bubble is quickly discharged conducive to electrode surface, it is possible to reduce bubble avoids the increasing of electrode overpotential in the Long-Term Sorption of electrode surface
Add.
3. the hydrogen-precipitating electrode in the present invention is integrated hydrogen-precipitating electrode, compare Fine carbides catalyst, which makes
With the use for the conductive agent and binder for avoiding traditional electrode in the process, the material cost and electrode system of hydrogen-precipitating electrode are reduced
Standby difficulty, and the stability of hydrogen-precipitating electrode is improved, in 0.5M H2SO4Solution continuous electrolysis 100h is without there is electric current
It reduces.Relative to the nickel-base alloy hydrogen-precipitating electrode now industrially applied, which has preferable liberation of hydrogen catalytic effect, in 0.5M
H2SO4In 100mA cm in solution-2When current density electrolysis, overpotential of hydrogen evolution is only 183.5mV；In 1M KOH solution
100mA cm-2When current density electrolysis, overpotential of hydrogen evolution 157.8mV；In 1M Na2SO4In in 100mA cm-2Current density
When electrolysis, overpotential 553.8mV.The electrode realizes the liberation of hydrogen of small overpotential electrolysis water under the high current density of full pH range
Effect, liberation of hydrogen LSV are as shown in Figure 4.
4. the present invention can be prepared by " a step fused carbonate electrolysis method " with the more of honeycomb microstructure
Orifice carbide hydrogen-precipitating electrode, the preparation method is easy to operate, environmentally protective, and controllability is strong, and metal used is not noble metal event
Cost is relatively low, has large-scale application prospect.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects, features and advantages of the invention can
It is clearer and more comprehensible, below in conjunction with preferred embodiment, detailed description are as follows.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues.
Fig. 1 is the optical picture of the porous carbide hydrogen-precipitating electrode of the present invention with honeycomb microstructure；
Fig. 2 is that the surface microscopic SEM of the porous carbide hydrogen-precipitating electrode of the present invention with honeycomb microstructure schemes；
Fig. 3 is deionized water on the porous carbide hydrogen-precipitating electrode surface of the present invention with honeycomb microstructure
Contact angle test figure；
Fig. 4 is the porous carbide hydrogen-precipitating electrode of the present invention with honeycomb microstructure in acidity (H2SO4), alkali
Property (KOH) and neutrality (Na2SO4) polarization curve in aqueous solution.
Specific embodiment
The following detailed description of a specific embodiment of the invention, as part of this specification, by embodiment come
Illustrate that the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Case study on implementation 1
It weighs the total 500g of NaF-KF that molar ratio is 39:61 and Na is added2CO325g prepares mixing and is put in alumina crucible,
It is placed in 48h in 200 DEG C of drying boxes and removes wherein moisture, taking-up is put into high temperature resistance furnace, with 3 DEG C/min liter under argon atmosphere protection
Warm speed is increased to 800 DEG C, keeps the temperature 3h.Insertion specification be 10mm × 10mm × 1mmW piece be cathode (W piece surface by 300#,
600# carborundum paper polishing, then by dehydrated alcohol, acetone, deionized water ultrasonic cleaning), graphite rod is anode, with
1.2V slot piezoelectricity solution 3h after electrolysis, proposes electrode to fused salt ullage 20min, until cooling, taking-up is put into deionization
Water be cleaned by ultrasonic 30min, obtain the porous carbide hydrogen-precipitating electrode with honeycomb microstructure, wherein carbide include WC and
W2C, porous silicon carbide tungsten coating thickness are 10 μm, and pore size range is 20~100nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4Exist with 1M KOH system
100mA cm-2Overpotential when current density is respectively 188.3mV, 682mV and 163.5mV, in 30mA cm-2Under current density
Continuous electrolysis 200h, overpotential do not increase.
Case study on implementation 2
Weigh the K that molar ratio is 50:502CO3-Li2CO3Total 500g prepares mixing and is put in alumina crucible, is placed in 200 DEG C
48h removes wherein moisture in drying box, and taking-up is put into high temperature resistance furnace, with 3 DEG C of min under argon atmosphere protection-1Heating rate liter
Up to 750 DEG C, keep the temperature 3h.Insertion 10mm × 10mm × 0.2mm Mo piece is that (300#, 600# silicon carbide are passed through in Mo piece surface to cathode
Sand paper polishing, then by dehydrated alcohol, acetone, deionized water ultrasonic cleaning), graphite rod is anode, with 5mA cm-2Constant current
Be powered electrolysis 1.5h, after electrolysis, proposes electrode to fused salt ullage 20min, until cooling, taking-up is put into deionized water
Be cleaned by ultrasonic 30min, obtain the porous carbide hydrogen-precipitating electrode with honeycomb microstructure, wherein carbide include MoC and
Mo2C, stephanoporate molybdenum carbide coating layer thickness are 7 μm, and pore size range is 20~50nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4Exist with 1M KOH system
100mA cm-2Overpotential when current density is respectively 207.5mV, 592.6mV and 196.5mV, continuous under 150mV overpotential
It is electrolysed 300h, electric current does not reduce.
Case study on implementation 3
Weigh CaCl2Total 500g simultaneously adds CaCO320g prepares mixing and is put in alumina crucible, is placed in 300 DEG C of drying boxes
Middle 48h removes wherein moisture, and taking-up is put into high temperature resistance furnace, with 3 DEG C of min under argon atmosphere protection-1Heating rate is increased to 780
DEG C, keep the temperature 4h.Insertion 10mm × 10mm × 2mm Mo piece be cathode (Mo piece surface by 300#, 600# carborundum paper polishing,
Then by dehydrated alcohol, acetone, deionized water ultrasonic cleaning), graphite rod is anode, with 0.5V slot piezoelectricity solution 3h, electrolysis knot
Shu Hou proposes electrode to fused salt ullage 20min, until cooling, taking-up is put into deionized water ultrasonic cleaning 30min, obtains
Porous carbide hydrogen-precipitating electrode with honeycomb microstructure, wherein carbide includes MoC and Mo2C, surface layer stephanoporate molybdenum carbide
Coating layer thickness is 13 μm, and pore size range is 10~60nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4Exist with 1M KOH system
100mA cm-2Overpotential when current density is respectively 197.5mV, 598.3mV and 176.9mV, continuous under 150mV overpotential
It is electrolysed 350h, electric current does not reduce.
Case study on implementation 4
Weigh the Na that molar ratio is 43.5:31.5:252CO3-K2CO3-Li2CO3Total 500g prepares mixing and is put in aluminium oxide
Crucible is placed in 48h in 300 DEG C of drying boxes and removes wherein moisture, and taking-up is put into high temperature resistance furnace, with 3 DEG C under argon atmosphere protection
min-1Heating rate is increased to 750 DEG C, keeps the temperature 4h.Insertion Ti piece is that (300#, 600# carborundum paper are passed through in Ti piece surface to cathode
Polishing, then by dehydrated alcohol, acetone, deionized water ultrasonic cleaning), ferronickel copper alloy is inert anode, with 5mA cm-2It is permanent
Current electroanalysis 4h after electrolysis, proposes electrode to fused salt ullage 20min, until cooling, it is super that taking-up is put into deionized water
Sound cleans 30min, obtains the porous carbide hydrogen-precipitating electrode with honeycomb microstructure, and wherein carbide is TiC, applies thickness
Degree is 11 μm, and pore size is 12~55nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4With in 1M KOH system
100mA cm-2Overpotential when current density is respectively 286.3mV, 792.6mV and 267.4mV, continuous under 150mV overpotential
It is electrolysed 300h, electric current does not reduce.
Case study on implementation 5
Weigh Li2CO3Total 500g prepares mixing and is put in alumina crucible, is placed in 48h in 300 DEG C of drying boxes and removes wherein water
Point, taking-up is put into high temperature resistance furnace, with 3 DEG C of min under argon atmosphere protection-1Heating rate is increased to 750 DEG C, keeps the temperature 4h.Insertion
10mm × 10mm × 2mm W-Mo alloy sheet is that cathode (polish by 300#, 600# carborundum paper, so by W-Mo alloy sheet surface
It is cleaned by ultrasonic afterwards by dehydrated alcohol, acetone, deionized water), graphite rod is anode, with 2mA cm-2Constant-current electrolysis 3.5h, electricity
After solution, propose that electrode takes out until cooling to fused salt ullage 20min and is put into deionized water ultrasonic cleaning 30min,
The porous carbide hydrogen-precipitating electrode with honeycomb microstructure is obtained, wherein carbide includes WC, MoC, Mo2C, coating layer thickness
It is 15 μm, pore size is 20~60nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4Exist with 1M KOH system
100mA cm-2Overpotential when current density is respectively 183.5mV, 553.8mV and 157.8mV, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Case study on implementation 6
It weighs the total 500g of NaCl-KCl that molar ratio is 50:50 and adds Li2CO320g prepares mixing and is put in aluminium oxide earthenware
Crucible is placed in 48h in 300 DEG C of drying boxes and removes wherein moisture, and taking-up is put into high temperature resistance furnace, with 3 DEG C under argon atmosphere protection
min-1Heating rate is increased to 900 DEG C, keeps the temperature 4h.Insertion 10mm × 10mm × 0.2mm Mo-Ti alloy sheet is cathode (Mo-Ti
Alloy sheet surface is polished by 300#, 600# carborundum paper, then clear by dehydrated alcohol, acetone, deionized water ultrasound
Wash), graphite rod is anode, with 3mA cm-2Constant-current electrolysis 2h after electrolysis, proposes electrode to fused salt ullage
20min, until cooling, taking-up is put into deionized water ultrasonic cleaning 30min, as with the porous silicon carbide of honeycomb microstructure
Object hydrogen-precipitating electrode, wherein carbide includes Mo2C and TiC, coating layer thickness are 50 μm, and pore size is 10~30nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4With in 1M KOH system
100mA cm-2Overpotential when current density is respectively 195.5mV, 573.3mV and 167.4mV, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Case study on implementation 7
It weighs the total 500g of LiCl and adds 30g Na2CO3, prepare mixing and be put in alumina crucible, be placed in 300 DEG C of drying boxes
In remove wherein moisture for 24 hours, taking-up is put into high temperature resistance furnace, with 3 DEG C of min under argon atmosphere protection-1Heating rate is increased to 850
DEG C, keep the temperature 4h.Insertion diameter 5mmW-Ti alloy bar is that cathode (beat by 300#, 600# carborundum paper by W-Ti alloy bar surface
Mill, then by dehydrated alcohol, acetone, deionized water ultrasonic cleaning), graphite rod is anode, with -2.0V (vs.Ag/Ag2SO4)
Potentiostatic deposition 3h after electrolysis, proposes electrode to fused salt ullage 20min, until cooling, taking-up is put into deionized water
Be cleaned by ultrasonic 30min, obtain the porous carbide hydrogen-precipitating electrode with honeycomb microstructure, wherein carbide include WC and
TiC, coating layer thickness are 40 μm, and pore size is 10~30nm.
By the above-mentioned porous carbide hydrogen-precipitating electrode being prepared in 0.5M H2SO4、1M Na2SO4In 1M KOH system
In 100mA cm-2Overpotential is respectively 185.5mV, 596.3mV and 178.9mV when current density, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Case study on implementation 8
Weigh Li2CO3Total 500g prepares mixing and is put in alumina crucible, is placed in 48h in 300 DEG C of drying boxes and removes wherein water
Point, taking-up is put into high temperature resistance furnace, with 3 DEG C of min under argon atmosphere protection-1Heating rate is increased to 850 DEG C, keeps the temperature 4h.It is inserted into W
Piece is that cathode (polish by 300#, 600# carborundum paper, then super by dehydrated alcohol, acetone, deionized water by W piece surface
Sound cleaning), graphite rod is anode, with 3mA cm-2Constant-current electrolysis 2h after electrolysis, proposes electrode to fused salt ullage
20min, until cooling, taking-up is put into deionized water ultrasonic cleaning 30min, obtains the porous silicon carbide with honeycomb microstructure
Object hydrogen-precipitating electrode, wherein carbide is WC, and coating layer thickness is 33 μm, and pore size is 20~45nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4With in 1M KOH system
100mA cm-2Overpotential when current density is respectively 225.9mV, 623.3mV and 193.2mV, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Case study on implementation 9
It weighs the total 500g of NaF-KF that molar ratio is 39:61 and adds Li2CO350g prepares mixing and is put in aluminium oxide earthenware
Crucible is placed in 48h in 300 DEG C of drying boxes and removes wherein moisture, and taking-up is put into high temperature resistance furnace, with 3 DEG C under argon atmosphere protection
min-1Heating rate is increased to 850 DEG C, keeps the temperature 4h.The stainless steel substrates that W coating is contained on insertion surface are that cathode (contains W painting in surface
The stainless steel substrates surface of layer is polished by 300#, 600# carborundum paper, then super by dehydrated alcohol, acetone, deionized water
Sound cleaning), graphite rod is anode, with 3mA cm-2Constant-current electrolysis 2h after electrolysis, proposes electrode to fused salt ullage
20min, until cooling, taking-up is put into deionized water ultrasonic cleaning 30min, obtains the porous silicon carbide with honeycomb microstructure
Object hydrogen-precipitating electrode, wherein carbide is WC, and coating layer thickness is 15 μm, and pore size is 30~80nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4With in 1M KOH system
100mA cm-2Overpotential when current density is respectively 203.3mV, 593.1mV and 185.6mV, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Case study on implementation 10
Weigh the Na that molar ratio is 43.5:31.5:252CO3-K2CO3-Li2CO3Total 500g prepares mixing and is put in aluminium oxide
Crucible is placed in 48h in 300 DEG C of drying boxes and removes wherein moisture, and taking-up is put into high temperature resistance furnace, with 3 DEG C under argon atmosphere protection
min-1Heating rate is increased to 800 DEG C, keeps the temperature 4h.The stainless steel substrates that Mo-W coating is contained on insertion surface are that cathode (contains on surface
The stainless steel substrates surface of Mo-W coating by 300#, 600# carborundum paper polish, then by dehydrated alcohol, acetone, go from
Sub- water ultrasonic cleaning), graphite rod is anode, with 3.5mA cm-2Constant-current electrolysis 3h after electrolysis, proposes electrode to fused salt
Ullage 20min, until cooling, taking-up is put into deionized water ultrasonic cleaning 30min, obtains having honeycomb microstructure
Porous carbide hydrogen-precipitating electrode, wherein carbide is WC, and coating layer thickness is 12 μm, and pore size is 30~60nm.
The above-mentioned porous carbide hydrogen-precipitating electrode being prepared is in 0.5M H2SO4、1M Na2SO4With in 1M KOH system
100mA cm-2Overpotential when current density is respectively 193.0mV, 567.3mV and 177.5mV, continuous under 150mV overpotential
It is electrolysed 400h, electric current does not reduce.
Fig. 1 is the optical photograph of the porous carbide hydrogen-precipitating electrode with honeycomb microstructure.It can be with from figure
Find out that the porous carbide hydrogen-precipitating electrode with honeycomb microstructure of electrolytic preparation maintains complete surface structure, electrode
Surface is grey, and roughness with higher.
Fig. 2 is that the porous carbide hydrogen-precipitating electrode surface microscopic SEM with honeycomb microstructure schemes.It can from figure
To find out the electrode surface microscopic appearance as cellular structures, which is capable of providing more hydrogen evolution activity sites, subtracts
The screen effect of few bubble, improves the hydrogen evolution activity of electrode.
Fig. 3 is that deionized water is surveyed in the porous carbide hydrogen-precipitating electrode surface contact angle with honeycomb microstructure
Attempt.As can be seen from the figure the hydrogen-precipitating electrode and water of this method preparation have preferable wetability.
Fig. 4 is the porous carbide hydrogen-precipitating electrode with honeycomb microstructure in acidity (H2SO4), alkaline (KOH)
And neutrality (Na2SO4) polarization curve in aqueous solution.Figure 4, it is seen that the electrode realizes the big electricity of full pH range
The liberation of hydrogen effect of small overpotential electrolysis water under current density.
The bound of each raw material cited by the present invention and each raw material of the present invention, section value and technological parameter
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of porous carbide hydrogen-precipitating electrode with honeycomb microstructure, it is characterised in that: including can carburizing type metal
Substrate and porous carbide coating with honeycomb microstructure.
2. as described in claim 1 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that: described
Porous carbide coating layer thickness is 0.01 μm~200 μm, and porous carbide coating aperture is 5nm~500nm.
3. as claimed in claim 2 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that: described
Porous carbide coating layer thickness is 1 μm~50 μm, is further 11 μm~50 μm, and porous carbide coating aperture is 12nm
~80nm.
4. as claimed in claim 1 or 2 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that:
It is described can carburizing type metal include W, Mo, Ti and its alloy, or the metal or alloy containing W, Mo, Ti and its alloy coat.
5. as claimed in claim 4 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that: described
Carbide coating is metal-carbide coating, and the metal-carbide coating group becomes MC and/or M2C, M refer to W, Mo, Ti Dan Jin
Belong to the combination of element or any multiple element.
6. as described in claim 1 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that: described
The contact angle of hydrogen-precipitating electrode and water is 10 °~50 °.
7. as described in claim 1 with the porous carbide hydrogen-precipitating electrode of honeycomb microstructure, it is characterised in that: described
The shape of metallic substrates includes particle, sheet, rodlike, plate and cellular.
8. an a kind of one-step preparation method of the porous carbide hydrogen-precipitating electrode described in claim 1 with honeycomb microstructure,
It is characterized by comprising following steps: using fuse salt as electrolyte, using can carburizing type metal as cathode, with graphite electrode or
It is anode that inertia, which analyses oxygen electrode, applies voltage or current electroanalysis；Cathode is taken out after electrolysis, cleaning is removed residual fuse salt and obtained
To the porous carbide hydrogen-precipitating electrode containing honeycomb microstructure.
9. an one-step preparation method of the porous carbide hydrogen-precipitating electrode with honeycomb microstructure as claimed in claim 7,
Be characterized in that: the molten salt electrolyte is carbonate or the fuse salt containing carbonate, and the molten salt electrolyte includes
NaF-KF-Na2CO3、K2CO3-Li2CO3、CaCl2-Ca2CO3。
10. an one-step preparation method of the porous carbide hydrogen-precipitating electrode with honeycomb microstructure as claimed in claim 7,
Be characterized in that: the electrolysis mode is potentiostatic electrolysis or constant current electrolysis or permanent slot piezoelectricity solution, permanent slot pressure
Decomposition voltage is 0.1V~3.0V, and constant-current electrolysis current density is 0.1mA cm-2~500mA cm-2, potentiostatic deposition current potential
For -1.0V~-2.5V, reference electrode Ag/Ag2SO4, electrolysis temperature is 450 DEG C~900 DEG C, and electrolysis time is 0.1h~6h.
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