CN109252187A - A kind of high-entropy alloy elctro-catalyst, preparation method and the application of water decomposition hydrogen manufacturing - Google Patents
A kind of high-entropy alloy elctro-catalyst, preparation method and the application of water decomposition hydrogen manufacturing Download PDFInfo
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- CN109252187A CN109252187A CN201811051055.XA CN201811051055A CN109252187A CN 109252187 A CN109252187 A CN 109252187A CN 201811051055 A CN201811051055 A CN 201811051055A CN 109252187 A CN109252187 A CN 109252187A
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of high-entropy alloy elctro-catalyst, preparation method and the applications of water decomposition hydrogen manufacturing, belong to water decomposition hydrogen manufacturing energy field.High-entropy alloy elctro-catalyst, it is that electrochemical activation obtains after HF hydro-thermal process by high-entropy alloy CoCrFeNiAl piece, 80-150 DEG C of hydro-thermal process temperature.The elctro-catalyst is in 0.5M H2SO4The take-off potential of catalytic water decomposing hydrogen-production is -53mV (vs RHE) in solution, reaches 10mA cm‑2Current density only need overpotential 83mV, tower phenanthrene slope is 54.2mV/dec, and exchange current density is 0.312mA cm‑2。
Description
Technical field
The present invention relates to a kind of preparation methods of elctro-catalyst for water decomposition hydrogen manufacturing, belong to water decomposition hydrogen manufacturing energy neck
Domain.
Background technique
To reduce dependence of the mankind to fossil energy, the green energy resource of alternative fossil energy, electrocatalytic decomposition water are prepared
It produces hydrogen and has obtained the extensive concern of chemistry, material and environmental energy field.The research and development of efficient elctro-catalyst are then skills therein
Art is crucial.Metal platinum (Pt) is that electro-catalysis water decomposition so far prepares the superior catalyst of performance in hydrogen, is either existed
It can be used under conditions of acid and alkalinity.However it is with high costs and too low make it can not extensively in the content of the earth
With.Therefore the base metal of alternative Pt becomes Research Emphasis at this stage.In addition electro-catalysis water decomposition produces hydrogen in acid condition
Under activity than the high 2-3 order of magnitude under alkaline condition, develop non-precious metal catalyst that acid condition can be used more
Has practical significance.Nowadays there is good acid proof MoSP, MoS2And the metal nano material of other carbon materials protection is
There is the performance of good catalytic water decomposing hydrogen-production by report, but these elctro-catalysts still rely on conductive substrates material,
Electrode size can not be adjusted according to the actual situation, therefore can't be widely used.Exploitation has self supporting structure, electric conductivity
Well, the machinable metallic catalyst of size can accelerate the adjustment of modern society's energy resource structure, significant.In R&D process most
Big technological challenge is exactly the unstability in acidic electrolysis bath.
Alloy catalyst containing various metals has excellent catalytic activity due to coordination, geometric effect etc..Metal
It is doped to the electronic structure of regulation bulk catalyst, reduces the effective means of water decomposition dynamics energy barrier.At interface after doping
The catalyzing atom rearranged can regulate and control electron transmission, generate the effects such as lattice strain, so as to improve the performance of catalyst.Invention
Content
The purpose of the present invention is to provide a kind of high-entropy alloy elctro-catalyst, preparation method and the applications of water decomposition hydrogen manufacturing.
To achieve the goals above, the technical solution used in the present invention is:
High-entropy alloy elctro-catalyst, it is obtained after high-entropy alloy CoCrFeNiAl piece is added HF hydro-thermal process, hydro-thermal
80-150 DEG C for the treatment of temperature.
According to the above scheme, HF solution concentration 0.04-0.4M, hydrothermal conditions 2-10 hours.Concentration, the hydro-thermal of HF solution
Treatment temperature and hydrothermal conditions are an important factor for influencing high-entropy alloy catalytic effect.HF concentration and hydro-thermal reaction temperature
Height is spent, the hydro-thermal reaction time is too long, keeps the reaction rate of HF and high-entropy alloy too fast, so that the alloy on surface layer is easy to be excessive
Low-alloyed catalytic performance, can drop in corrosion instead.
According to the above scheme, HF treated high-entropy alloy piece is subjected to electrochemical activation, the electrochemical activation are as follows: logical
It crosses Ampere currents method to activate in three-electrode system, electrolyte is 0.1-1M H2SO4Solution, boost voltage are -125-50mV (vs
RHE), activation time 4-24h.Method particularly includes: HF treated high-entropy alloy piece conductive silver glue is connected into upper conducting wire, so
It uses insulating cement electrode coated afterwards and the reverse side of the junction of conducting wire, elargol and electrode, working electrode is obtained after dry, is saturated sweet
For mercury electrode as reference electrode, carbon-point is to establish three-electrode system to electrode, using Ampere currents method, voltage is arranged, to work
Electrode carries out electrochemical activation, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.High-entropy alloy elctro-catalyst
Preparation method, it includes the following steps:
1) CoCrFeNiAl high-entropy alloy (H-alloy) block the pre-treatment of high-entropy alloy piece: is cut into sheet；
2) post-processing of high-entropy alloy piece: CoCrFeNiAl piece is added into HF hydro-thermal process, obtains HF- alloy, hydro-thermal process
80-150 DEG C of temperature；
3) HF- alloy the electrochemical activation of high-entropy alloy piece: is subjected to electrochemical activation.
According to the above scheme, the CoCrFeNiAl high-entropy alloy (H-alloy) passes through high-energy ball milling and plasma discharging
Body sintering preparation, method particularly includes: five kinds of metals of Co, Cr, Fe, Ni, Al are put into ball milling in ball mill, each metal in alloy
The proportion of Co, Cr, Fe, Ni, Al meet the requirement for forming Alloy solid solution；Alloyed powder after ball milling is burnt by discharge plasma
The mode of knot sinters CoCrFeNiAl high-entropy alloy block into, and sintering temperature is 900-1100 DEG C, sintering pressure 30-50MPa,
Sintering time is 5-10min.
According to the above scheme, the molar ratio of each metal Co, Cr, Fe, Ni, Al can be 1:1:1:1:1.Each metal Co, Cr, Fe,
The proportion of Ni, Al are not limited to equimolar ratio, if can be formed Alloy solid solution high-entropy alloy can time method obtain height
The catalytic water decomposition hydrogen producing catalyst of effect.
According to the above scheme, the ball milling abrasive material is stainless steel ball, and ratio of grinding media to material 15:1 is added normal heptane and does grinding aid,
It is passed through argon gas and does protective gas, revolving speed 250rpm, the spheroidal graphite time is 60h.
The application in efficient catalytic water decomposition hydrogen manufacturing in acid condition of above-mentioned CoCrFeNiAl high-entropy alloy elctro-catalyst.
Application method are as follows: using above-mentioned carry out HF handle and electrochemical activation after CoCrFeNiAl high-entropy alloy piece as working electrode,
For saturated calomel electrode as reference electrode, carbon-point is to establish three-electrode system to electrode, carries out efficient catalytic water decomposition hydrogen manufacturing.
According to the above scheme, the electrolyte in electrochemical system is 0.1-1M H2SO4Solution, boost voltage are -125-50mV
(vs RHE)。
The high-entropy alloy elctro-catalyst of this patent is different from conventional metal alloy, the maximization of high-entropy alloy medium entropy so that
Phase structure is more stable.Mutually doping leads to distortion of lattice between each metal in alloy, and in addition the addition of Cr and Al leads to chicken tail
Wine effect makes high-entropy alloy have excellent corrosion resistance characteristic.High-entropy alloy itself has the structure of self-supporting, does not need to lead
Electric substrate has excellent electric conductivity, has these behavioral illustrations high-entropy alloys such as corrosion resistance can in acid electrolyte
To be used in acid condition as catalyst.More important point is exactly that the reservation of the nanometer phase in high-entropy alloy can be electricity
Catalytic process provides active site abundant.
HF hydro-thermal process is passed through in cooperation on the basis of the above, and the alloy surface shows porous structure after hydro-thermal process,
The metallic atom for more having catalytic action can be exposed to participation catalysis reaction, so that the transmitting of electrolyte and electronics
Faster, to significantly improve the catalytic effect of catalyst.
For the high-entropy alloy that HF is handled in this patent in three-electrode system, application voltage is -125mV (vs RHE),
0.5M H2SO4The chrono-amperometric test that 24 hours are carried out in solution, finds 10mAcm of the current density from beginning-2First reduce, it is several
It begins to gradually increase after minute, just tends towards stability within about 21 hours, illustrate that the electrode experienced the process of an electrochemical activation.
The activation is so that it is original 2.4 times that current density, which increases,.The elctro-catalyst is in 0.5M H after activation2SO4Moisture is catalyzed in solution
The take-off potential of solution hydrogen manufacturing is just being moved on to -53mV (vs RHE) by -70mV, reaches 10mA cm-2Overpotential be reduced to by 125
83mV, tower phenanthrene slope are reduced to 54.2mV/dec by 74.2, and it is 0.312mA cm that exchange current density is increased by 0.216-2.With it is existing
There is technology to compare, the beneficial effects of the present invention are:
1, the catalyst is the CoCrFeNiAl high-entropy alloy of Fe, Co, Ni, Cr and Al element composition of low cost, is had
The structure of self-supporting can be processed into different sizes.Suitable size can be such as cut by the method for wire cutting, it is easy to use.
2, the catalyst is obtained by the method for carrying out HF processing and electrochemical activation to CoCrFeNiAl high-entropy alloy, is located
Reason method is simple, and electrocatalysis characteristic is efficient.The CoCrFeNiAl high-entropy alloy piece of self-supporting is used as in acidity by the present invention for the first time
Under the conditions of water decomposition hydrogen manufacturing elctro-catalyst, the elctro-catalyst is in 0.5M H2SO4The starting electricity of catalytic water decomposing hydrogen-production in solution
Position is -53mV (vs RHE), reaches 10mA cm-2Current density only need overpotential 83mV, tower phenanthrene slope is 54.2mV/
Dec, better than elctro-catalysts such as CoNi@NC (Angew.Chem.Int.Ed.2015,54,2100-2104) reported in the literature.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of CoCrFeNiAl high-entropy alloy elctro-catalyst in the embodiment of the present invention 1.
Fig. 2 is SEM pattern picture of the CoCrFeNiAl high-entropy alloy in HF before and after the processing in the embodiment of the present invention 1, a processing
Before, after b processing.
Fig. 3 is XRD diagram piece of the CoCrFeNiAl high-entropy alloy in HF before and after the processing in the embodiment of the present invention 1.XRD result is said
The high-entropy alloy of bright this patent preparation is by FCC and BCC phase composition, on the structure composition of alloy without influence after HF processing.
Fig. 4 is CoCrFeNiAl high-entropy alloy HF processing in the embodiment of the present invention 1 and the electrification before and after electrochemical activation
Learn polarization curve.Catalyst is respectively high-entropy alloy, the high-entropy alloy (HF- alloy) of HF processing, by electrochemical treatments when 24
HF- high-entropy alloy, and commercialization 20%wt-Pt/C electrode, the scanning speed of polarization curve are 5mVs-1, in polarization curve
Each voltage is relative to reversible hydrogen electrode.
Fig. 5 is the j-t curve of CoCrFeNiAl high-entropy alloy after HF processing in the embodiment of the present invention 1.
Specific embodiment
For a better understanding of the present invention, with reference to the accompanying drawing, the embodiment content that the present invention is furture elucidated, but this hair
Bright content is not limited solely to the following examples.
Embodiment 1
A kind of preparation method of the CoCrFeNiAl high-entropy alloy elctro-catalyst with efficient catalytic water decomposition hydrogen manufacturing, it is wrapped
Include following steps:
1) pre-treatment of high-entropy alloy piece:
The CoCrFeNiAl high-entropy alloy block (H-alloy) prepared by high-energy ball milling and discharge plasma sintering,
The preparation method comprises the following steps: five kinds of metals of Co, Cr, Fe, Ni, Al are put into ball milling in ball mill, each metal Co, Cr in alloy, Fe, Ni,
The molar ratio of Al is 1:1:1:1:1, and ball milling abrasive material is stainless steel ball, and ratio of grinding media to material 15:1 is added normal heptane and does grinding aid, is passed through
Argon gas does protective gas, revolving speed 250rpm, and the spheroidal graphite time is 60h, and the alloyed powder after ball milling is sintered by discharge plasma
Mode sinter CoCrFeNiAl high-entropy alloy block into, sintering temperature is 950 DEG C, sintering pressure 50MPa, and sintering time is
10min obtains CoCrFeNiAl high-entropy alloy block (H-alloy)；
The CoCrFeNiAl high-entropy alloy block (H-alloy) of high-energy ball milling and discharge plasma sintering preparation will be passed through
Being cut into surface area with the mode of wire cutting is 0.29cm2Fanning strip, thickness is about 2mm.
2) post-processing of high-entropy alloy piece: CoCrFeNiAl fanning strip is put into the water heating kettle of the polytetrafluoroethylene (PTFE) of 50mL
In gallbladder, the HF solution 20mL of 0.04M is then added, water heating kettle liner is put into stainless steel casing, after sealing, is put into baking oven
In, setting temperature is 90 DEG C, 5 hours of hydro-thermal process, alloy sheet is taken out, after being cleaned up with deionized water, at room temperature
Naturally dry.The alloy designations are HF- alloy.The SEM pattern picture of HF before and after the processing is shown in Fig. 2, and Fig. 2 is it can be seen that with HF
Before processing, alloy surface structure is finer and close, and after being handled with HF, porous structure is presented in surface.This is conducive to catalytic process
The quick transmission of middle electronics and electrolyte.
3) electrochemical activation of high-entropy alloy piece: HF- alloy conductive silver glue is connected into upper conducting wire, is then applied with insulating cement
Junction, elargol and the electrode reverse side for covering electrode and conducting wire, as working electrode after waiting glue dry, using saturated calomel electrode
As reference electrode, carbon-point is to electrode, and electrolyte is 0.5M H2SO4Solution establishes three-electrode system, in occasion China electrochemistry work
It is operated on standing, using Ampere currents method, setting voltage is -125mV (vs RHE), and it is living to carry out electrochemistry to working electrode
Change, activation time is for 24 hours, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.
The test that polarization curve is carried out to the working electrode before and after electrochemical activation, is shown in Fig. 4, is catalyzed from polarization curve
The take-off potential of water decomposition, current density are 10mA cm-2Overpotential, Tafel slope and exchange current density etc. key number
According to.And test the stability of HF- alloy elctro-catalyst.The elctro-catalyst is in 0.5M H after activation2SO4Water decomposition is catalyzed in solution
The take-off potential of hydrogen manufacturing is just being moved on to -53mV (vs RHE) by -70mV, reaches 10mA cm-2Current density overpotential by 125
It is reduced to 83mV, tower phenanthrene slope is reduced to 54.2mV/dec by 74.2, and it is 0.312mA that exchange current density is increased by 0.216
cm-2.Therefore the catalytic performance of HF- high-entropy alloy significantly improves.
The application of catalytic water decomposing hydrogen-production: the catalyst after activation completes catalysis water decomposition system equally in three-electrode system
The performance test of hydrogen, carbon-point are to electrode, and high-entropy alloy piece is working electrode, and saturated calomel electrode is reference electrode.Polarization is bent
The test electrolyte of line is similarly 0.5M H2SO4Solution, the scanning speed of polarization curve are 5mVs-1.Wherein all potentials are all
Relative to reversible hydrogen electrode.
The j-t curve of CoCrFeNiAl high-entropy alloy is shown in Fig. 5 after HF processing.As seen from Figure 5, just start current density
By 10mAcm-2Rapid decay is to 6.5mAcm-2, but went up rapidly at 2 minutes, then continue to increase, electric current is close after 21 hours
Degree reaches 24mAcm-2, then electric current holding is stablized constant.
Embodiment 2
A kind of preparation method of the CoCrFeNiAl high-entropy alloy elctro-catalyst with efficient catalytic water decomposition hydrogen manufacturing, it is wrapped
Include following steps:
1) preparation method and embodiment 1 of CoCrFeNiAl high-entropy alloy block is identical.
2) CoCrFeNiAl of high-energy ball milling and discharge plasma sintering preparation the pre-treatment of high-entropy alloy piece: will be passed through
It is 0.29cm that high-entropy alloy block (H-alloy), which is cut into surface area with the mode of wire cutting,2Fanning strip, thickness is about 2mm.
3) post-processing of high-entropy alloy piece: CoCrFeNiAl fanning strip is put into the water heating kettle of the polytetrafluoroethylene (PTFE) of 50mL
In gallbladder, the HF solution 20mL of 0.4M is then added, water heating kettle liner is put into stainless steel casing, after sealing, is put into baking oven,
It is 90 DEG C that temperature, which is arranged, 5 hours of hydro-thermal process, alloy sheet is taken out, natural at room temperature after being cleaned up with deionized water
It dries.The alloy designations are HF- alloy.
4) electrochemical activation of high-entropy alloy piece: HF- alloy conductive silver glue is connected into upper conducting wire, is then applied with insulating cement
Junction, elargol and the electrode reverse side for covering electrode and conducting wire, as working electrode after waiting glue dry, using saturated calomel electrode
As reference electrode, carbon-point is to electrode, and electrolyte is 0.5M H2SO4Solution establishes three-electrode system, in occasion China electrochemistry work
It is operated on standing, using Ampere currents method, setting voltage is -125mV (vs RHE), and it is living to carry out electrochemistry to working electrode
Change, activation time is for 24 hours, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.
The HF- alloy is in 10mAcm-2Overpotential be 135mV, after electrochemical activation, which shuffles 20mV, property
It can be optimized.
Embodiment 3
A kind of preparation method of the CoCrFeNiAl high-entropy alloy elctro-catalyst with efficient catalytic water decomposition hydrogen manufacturing, it is wrapped
Include following steps:
1) preparation method and embodiment 1 of CoCrFeNiAl high-entropy alloy block is identical.
2) CoCrFeNiAl of high-energy ball milling and discharge plasma sintering preparation the pre-treatment of high-entropy alloy piece: will be passed through
It is 0.29cm that high-entropy alloy block (H-alloy), which is cut into surface area with the mode of wire cutting,2Fanning strip, thickness is about 2mm.
3) post-processing of high-entropy alloy piece: CoCrFeNiAl fanning strip is put into the water heating kettle of the polytetrafluoroethylene (PTFE) of 50mL
In gallbladder, the HF solution 20mL of 0.04M is then added, water heating kettle liner is put into stainless steel casing, after sealing, is put into baking oven
In, setting temperature is 120 DEG C, and hydro-thermal process 5h takes out alloy sheet, natural at room temperature after being cleaned up with deionized water
It dries.The alloy designations are HF- alloy.
4) electrochemical activation of high-entropy alloy piece: HF- alloy conductive silver glue is connected into upper conducting wire, is then applied with insulating cement
Junction, elargol and the electrode reverse side for covering electrode and conducting wire, as working electrode after waiting glue dry, using saturated calomel electrode
As reference electrode, carbon-point is to electrode, and electrolyte is 0.5M H2SO4Solution establishes three-electrode system, in occasion China electrochemistry work
It is operated on standing, using Ampere currents method, setting voltage is -125mV (vs RHE), and it is living to carry out electrochemistry to working electrode
Change, activation time 12h, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.
The high-entropy alloy is in 10mAcm-2Overpotential be 132mV, after electrochemical activation, which shuffles 15mV, property
It can be optimized.
Embodiment 4
A kind of preparation method of the CoCrFeNiAl high-entropy alloy elctro-catalyst with efficient catalytic water decomposition hydrogen manufacturing, it is wrapped
Include following steps:
1) preparation method and embodiment 1 of CoCrFeNiAl high-entropy alloy block is identical.
2) CoCrFeNiAl of high-energy ball milling and discharge plasma sintering preparation the pre-treatment of high-entropy alloy piece: will be passed through
It is 0.29cm that high-entropy alloy block (H-alloy), which is cut into surface area with the mode of wire cutting,2Fanning strip, thickness is about 2mm.
3) post-processing of high-entropy alloy piece: CoCrFeNiAl fanning strip is put into the water heating kettle of the polytetrafluoroethylene (PTFE) of 50mL
In gallbladder, the HF solution 20mL of 0.04M is then added, water heating kettle liner is put into stainless steel casing, after sealing, is put into baking oven
In, setting temperature is 90 DEG C, 10 hours of hydro-thermal process, alloy sheet is taken out, after being cleaned up with deionized water, at room temperature
Naturally dry.The alloy designations are HF- alloy.
4) electrochemical activation of high-entropy alloy piece: HF- alloy conductive silver glue is connected into upper conducting wire, is then applied with insulating cement
Junction, elargol and the electrode reverse side for covering electrode and conducting wire, as working electrode after waiting glue dry, using saturated calomel electrode
As reference electrode, carbon-point is to electrode, and electrolyte is 0.5M H2SO4Solution establishes three-electrode system, in occasion China electrochemistry work
It is operated on standing, using Ampere currents method, setting voltage is -125mV (vs RHE), and it is living to carry out electrochemistry to working electrode
Change, activation time is for 24 hours, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.
The high-entropy alloy is in 10mAcm-2Overpotential be 190mV, after electrochemical activation, which shuffles 30mV, property
It can be optimized.
Embodiment 5
A kind of preparation method of the CoCrFeNiAl high-entropy alloy elctro-catalyst with efficient catalytic water decomposition hydrogen manufacturing, it is wrapped
Include following steps:
1) preparation method and embodiment 1 of CoCrFeNiAl high-entropy alloy block is identical.
2) CoCrFeNiAl of high-energy ball milling and discharge plasma sintering preparation the pre-treatment of high-entropy alloy piece: will be passed through
It is 0.29cm that the fast body of high-entropy alloy (H-alloy), which is cut into surface area with the mode of wire cutting,2Fanning strip, thickness is about 2mm.
3) post-processing of high-entropy alloy piece: CoCrFeNiAl fanning strip is put into the water heating kettle of the polytetrafluoroethylene (PTFE) of 50mL
In gallbladder, the HF solution 20mL of 0.04M is then added, water heating kettle liner is put into stainless steel casing, after sealing, is put into baking oven
In, setting temperature is 90 DEG C, 5 hours of hydro-thermal process, alloy sheet is taken out, after being cleaned up with deionized water, at room temperature
Naturally dry.The alloy designations are HF- alloy.
4) electrochemical activation of high-entropy alloy piece: HF- alloy conductive silver glue is connected into upper conducting wire, is then applied with insulating cement
Junction, elargol and the electrode reverse side for covering electrode and conducting wire, as working electrode after waiting glue dry, using saturated calomel electrode
As reference electrode, carbon-point is to electrode, and electrolyte is 0.5M H2SO4Solution establishes three-electrode system, in occasion China electrochemistry work
It is operated on standing, using Ampere currents method, setting voltage is -125mV (vs RHE), and it is living to carry out electrochemistry to working electrode
Change, activation time 12h, to obtain efficient CoCrFeNiAl high-entropy alloy elctro-catalyst.
The high-entropy alloy is in 10mAcm-2Overpotential be 125mV, after 12 hours electrochemical activations, the overpotential is just
18mV is moved, performance is optimized.
Various processing methods cited by the present invention can realize the present invention and each technical parameter bound value,
Interval value can realize the present invention, the bound value of technological parameter of the invention (such as hydro-thermal process temperature, activation time)
And interval value can realize the present invention, implementation numerous to list herein.
Claims (9)
1. high-entropy alloy elctro-catalyst, it is characterised in that: it is to add HF hydro-thermal process to obtain high-entropy alloy CoCrFeNiAl piece
, 80-150 DEG C of hydro-thermal process temperature.
2. high-entropy alloy elctro-catalyst according to claim 1, it is characterised in that: HF solution concentration 0.04-0.4M, hydro-thermal
Processing time 2-10 hours.
3. high-entropy alloy elctro-catalyst according to claim 1, it is characterised in that: high-entropy alloy elctro-catalyst is carried out electricity
Chemical activation, the electrochemical activation are as follows: by HF treated high-entropy alloy piece by Ampere currents method in three-electrode system
Middle activation, electrolyte are 0.1-1 M H2SO4Solution, the setting range of boost voltage are -125-50mV (vs RHE), when activation
Between be 4-24h.
4. the preparation method of high-entropy alloy elctro-catalyst described in claim 1, it is characterised in that: it includes the following steps:
1) CoCrFeNiAl high-entropy alloy (H-alloy) block the pre-treatment of high-entropy alloy piece: is cut into sheet；
2) post-processing of high-entropy alloy piece: CoCrFeNiAl piece is added into HF hydro-thermal process, obtains HF- alloy, hydro-thermal process temperature
80-150℃；
3) HF- alloy the electrochemical activation of high-entropy alloy piece: is subjected to electrochemical activation.
5. the preparation method of high-entropy alloy elctro-catalyst according to claim 4, it is characterised in that: described
CoCrFeNiAl high-entropy alloy (H-alloy) is prepared by high-energy ball milling and discharge plasma sintering, method particularly includes: it will
Five kinds of metals of Co, Cr, Fe, Ni, Al are put into ball milling in ball mill, and the proportion of each metal Co, Cr, Fe, Ni, Al meet shape in alloy
At the requirement of Alloy solid solution；Alloyed powder after ball milling sinters CoCrFeNiAl into such a way that discharge plasma is sintered
High-entropy alloy block, sintering temperature are 900-1100 DEG C, and sintering pressure is 30-50 MPa, and sintering time is 5-10 min.
6. the preparation method of high-entropy alloy elctro-catalyst according to claim 5, it is characterised in that: each metal Co, Cr,
The molar ratio of Fe, Ni, Al are 1:1:1:1:1.
7. the preparation method of high-entropy alloy elctro-catalyst according to claim 5, it is characterised in that: the ball milling mill
Material is stainless steel ball, and ratio of grinding media to material 15:1 is added normal heptane and does grinding aid, is passed through argon gas and does protective gas, revolving speed 250
Rpm, spheroidal graphite time are 60 h.
8. CoCrFeNiAl high-entropy alloy elctro-catalyst efficient catalytic water decomposition hydrogen manufacturing in acid condition described in claim 1
In application, application method are as follows: using above-mentioned carry out HF handle and electrochemical activation after CoCrFeNiAl high-entropy alloy piece as
Working electrode, for saturated calomel electrode as reference electrode, carbon-point is to establish three-electrode system to electrode, setting boost voltage is-
125-50 mV (vs RHE) carries out efficient catalytic water decomposition hydrogen manufacturing.
9. application according to claim 8, it is characterised in that: the electrolyte in electrochemical system is 0.1-1 M H2SO4It is molten
Liquid, boost voltage are -125-50 mV (vs RHE).
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| CN109999830A (en) * | 2019-05-05 | 2019-07-12 | 中国矿业大学 | Load C oCr(Mn/Al) FeNi high-entropy alloy nanoparticle catalyst and its preparation method and application |
| CN110079824A (en) * | 2019-05-17 | 2019-08-02 | 哈尔滨工业大学 | The method that high-energy ball milling prepares high-entropy alloy type electro-catalysis oxygen evolution reaction catalysts |
| CN110280255A (en) * | 2019-07-24 | 2019-09-27 | 东北大学秦皇岛分校 | A kind of nanometer of high-entropy alloy elctro-catalyst and preparation method thereof |
| CN110391092A (en) * | 2019-07-29 | 2019-10-29 | 南京工业大学 | High-entropy alloy nanometer frame, high-entropy alloy nanometer frame-manganese dioxide compound super capacitance electrode and its preparation |
| CN111074292A (en) * | 2020-02-18 | 2020-04-28 | 南昌航空大学 | Electro-catalytic hydrogen production porous high-entropy alloy electrode material and preparation method thereof |
| CN111774574A (en) * | 2020-07-20 | 2020-10-16 | 桂林电子科技大学 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
| CN112725818A (en) * | 2020-12-10 | 2021-04-30 | 西北工业大学 | Porous high-entropy alloy self-supporting electrode and method for electrolyzing water |
| CN113061925A (en) * | 2021-03-22 | 2021-07-02 | 北京科技大学 | Preparation method of hierarchical-pore high-entropy alloy water electrolysis catalyst |
| CN113511693A (en) * | 2021-07-19 | 2021-10-19 | 中国科学院兰州化学物理研究所 | Colored spinel type high-entropy oxide (NiFeCrM)3O4Synthesis method |
| CN113584516A (en) * | 2021-08-05 | 2021-11-02 | 哈尔滨工业大学 | High-entropy alloy fiber and preparation method and application thereof |
| CN113649035A (en) * | 2020-04-28 | 2021-11-16 | 武汉理工大学 | Molybdenum phosphide-based polycrystalline block and preparation method and application thereof |
| CN114420953A (en) * | 2021-12-29 | 2022-04-29 | 浙江大学 | Preparation method of silver/high-entropy hydroxide oxide nano composite material |
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| CN109999830B (en) * | 2019-05-05 | 2020-03-17 | 中国矿业大学 | CoCr (Mn/Al) FeNi high-entropy alloy-loaded nanoparticle catalyst and preparation method and application thereof |
| CN109999830A (en) * | 2019-05-05 | 2019-07-12 | 中国矿业大学 | Load C oCr(Mn/Al) FeNi high-entropy alloy nanoparticle catalyst and its preparation method and application |
| CN110079824A (en) * | 2019-05-17 | 2019-08-02 | 哈尔滨工业大学 | The method that high-energy ball milling prepares high-entropy alloy type electro-catalysis oxygen evolution reaction catalysts |
| CN110280255A (en) * | 2019-07-24 | 2019-09-27 | 东北大学秦皇岛分校 | A kind of nanometer of high-entropy alloy elctro-catalyst and preparation method thereof |
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| CN111074292A (en) * | 2020-02-18 | 2020-04-28 | 南昌航空大学 | Electro-catalytic hydrogen production porous high-entropy alloy electrode material and preparation method thereof |
| CN113649035A (en) * | 2020-04-28 | 2021-11-16 | 武汉理工大学 | Molybdenum phosphide-based polycrystalline block and preparation method and application thereof |
| CN111774574A (en) * | 2020-07-20 | 2020-10-16 | 桂林电子科技大学 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
| CN111774574B (en) * | 2020-07-20 | 2022-08-30 | 桂林电子科技大学 | Preparation and application of Al-Bi-containing compound porous block hydrogen production material |
| CN112725818A (en) * | 2020-12-10 | 2021-04-30 | 西北工业大学 | Porous high-entropy alloy self-supporting electrode and method for electrolyzing water |
| CN113061925A (en) * | 2021-03-22 | 2021-07-02 | 北京科技大学 | Preparation method of hierarchical-pore high-entropy alloy water electrolysis catalyst |
| CN113061925B (en) * | 2021-03-22 | 2022-02-22 | 北京科技大学 | Preparation method of hierarchical-pore high-entropy alloy water electrolysis catalyst |
| CN113511693A (en) * | 2021-07-19 | 2021-10-19 | 中国科学院兰州化学物理研究所 | Colored spinel type high-entropy oxide (NiFeCrM)3O4Synthesis method |
| CN113511693B (en) * | 2021-07-19 | 2023-03-14 | 中国科学院兰州化学物理研究所 | Colored spinel type high-entropy oxide (NiFeCrM) 3 O 4 Synthesis method |
| CN113584516A (en) * | 2021-08-05 | 2021-11-02 | 哈尔滨工业大学 | High-entropy alloy fiber and preparation method and application thereof |
| CN114420953A (en) * | 2021-12-29 | 2022-04-29 | 浙江大学 | Preparation method of silver/high-entropy hydroxide oxide nano composite material |
| CN114420953B (en) * | 2021-12-29 | 2023-03-10 | 浙江大学 | Preparation method of silver/high-entropy hydroxide oxide nano composite material |
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