CN108707922A - A kind of flexible nano is porous/amorphous composite material and preparation method thereof - Google Patents

A kind of flexible nano is porous/amorphous composite material and preparation method thereof Download PDF

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CN108707922A
CN108707922A CN201810416430.XA CN201810416430A CN108707922A CN 108707922 A CN108707922 A CN 108707922A CN 201810416430 A CN201810416430 A CN 201810416430A CN 108707922 A CN108707922 A CN 108707922A
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amorphous
composite material
porous
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nanoporous
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刘雄军
李睿
吕昭平
王辉
吴渊
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University of Science and Technology Beijing USTB
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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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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 propose a kind of flexible nano for water electrolysis hydrogen production it is porous/amorphous composite material and preparation method thereof.The composite material, as presoma, is taken off alloying selective removal Zr, Ti element by surface and is prepared with Ni-Zr-Ti- (Pt, Au, Pd) non-crystaline amorphous metal silk materials or strip.The nanocomposite has both the co-continuous nano-porous structure and amorphous state base layer of high-specific surface area, while having good mechanical flexibility, can 180 ° of arbitrary bendings.The composite material is directly used in electrolysis water hydrogen-precipitating electrode and shows excellent electrocatalytic properties of hydrogen evolution, and performance is substantially better than 10wt% business Pt/C catalyst.It can not only solve the brittleness problems of the porous electrocatalysis material generally existing of current block nanometer, it the shortcomings of traditional amorphous block can also be overcome, band specific surface area is not high and cause catalytic activity insufficient, has great application prospect in terms of high-performance electrolysis water hydrogen manufacturing electrode device.

Description

A kind of flexible nano is porous/amorphous composite material and preparation method thereof
Technical field
The invention belongs to clean sustainable energy application and preparation field, more particularly to a kind of flexibility for water electrolysis hydrogen production Nanoporous/amorphous composite material and preparation method thereof.
Background technology
With the aggravation of world energy sources crisis, tap a new source of energy extremely urgent.In numerous new energy, Hydrogen Energy conduct A kind of energy of high-efficiency cleaning got the attention and applies in 21 century.Electrolysis water evolving hydrogen reaction (HER：hydrogen Evolution reaction) it is to realize that industrialization inexpensively prepares the important means of hydrogen.Electrode material currently used for HER is general Store-through causes electrolysis electrode hydrogen-evolution overpotential excessively high, energy consumption the shortcomings of expensive, specific surface area is low, electro catalytic activity is not high It is excessive, seriously constrain the development of water electrolysis method hydrogen producing technology.To reduce cathode overpotential, energy consumption is reduced, exploitation has high HER The cathode hydrogen evolution material of catalytic activity has important scientific meaning and actual application value.
In recent years, the nano porous metal prepared using de- alloying is as a kind of emerging nanostructure function material Material, since it has the characteristics that high surface area, low-density, high-permeability, electric-conductivity heat-conductivity high, flexible structure are adjustable, shows A series of unique mechanics, physical and chemical properties, are expected to be widely used in fields such as catalysis, sensing, the energy.Its In, also by the extensive concern of researcher, various nano porous metals are (outstanding for application of the nano porous metal in terms of hydrolytic hydrogen production It is Pt, the noble metals such as Au, Pd) material shows excellent HER electro catalytic activities, although nano porous metal is in electro-catalysis Aspect has broad application prospects, but the nano porous metal block materials being prepared at present all lack flexibility, can not Function element is directly made, this severely limits practical application of the nano porous metal on electro catalytic electrode device.
Nano porous metal material common at present mainly uses crystal alloy to take off alloying and is prepared, due to crystalline state material Material is inevitably there are crystal defects such as crystal boundary, dislocations, these defects are easy to form crackle in de- alloying process, therefore The pore structure for the nano porous metal material being prepared by crystal alloy presoma is often all uneven, and lacks flexible. And for amorphous alloy, preparing nano porous metal as presoma alloy has its unique advantage：(1) non-crystaline amorphous metal With single phase composition (i.e. amorphous phase), be conducive to form uniform porous structure in de- alloy process；(2) multicomponent is non- The composition range of peritectic alloy is wider, and constituent element is adjustable, convenient for realizing the micro-structure tune of nano porous metal by design of alloy Control；(3) material shape diversity, other than common block materials, non-crystaline amorphous metal can also be made with good mechanical flexibility Strip and silk material.In recent years, it also emerges and much nano porous metal is prepared based on non-crystaline amorphous metal presoma and its is urged in electricity The report applied in terms of change, they show excellent electro catalytic activity.In addition, amorphous alloy itself is as a kind of metastable State material, thermodynamically energy be higher than crystal alloy, also show very high electro-chemical activity, therefore, amorphous alloy exists Application in terms of electrochemical catalysis is gradually paid attention to by researcher.Existing amorphous alloy material is answered in terms of hydrolytic hydrogen production at present Report, but we are had found by literature review, and non-crystaline amorphous metal is limited in that as catalytic electrode material：(1) at present Research object for electrocatalysis characteristic is mostly Pt, the noble metals base noncrystal alloy such as Au, Pd, as catalyst cost compared with It is high；(2) amorphous block, band specific surface area are smaller, and HER catalytic activity needs further to be promoted.Therefore non-crystaline amorphous metal conduct HER electrode materials remain many challenges.
Based on this, it is contemplated that advantage in terms of HER catalytic activity of nano porous metal and non-crystaline amorphous metal and respective Deficiency provides a kind of inexpensive combination electrode material with high HER catalytic activity can be directly used for electrode device and is being electrolysed Water hydrogen preparation field has important actual application value.
Invention content
It is an object of the invention to overcome the brittleness problems of the porous electrocatalysis material generally existing of current block nanometer and Traditional amorphous block, band specific surface is not high and the shortcomings of cause catalytic activity insufficient, provide a kind of for water electrolysis hydrogen production Flexible nano is porous/amorphous composite material and preparation method thereof.
Technical scheme is as follows：
A kind of flexible nano for water electrolysis hydrogen production is porous/amorphous composite material, the composite material is by high-specific surface area Co-continuous nano porous layer and noncrystal substrate layer composition, formed nanoporous active layer covering noncrystal substrate nano combined knot Structure；For the nanoporous layer thickness of the composite material in 200~500nm ranges, internal aperture size is 5~10nm.
Further, the nanoporous/amorphous composite material keeps good mechanical flexibility, can be arbitrary curved with 180 ° Song, easily prepared flexible electrode device.
Further, the nanoporous/amorphous composite material is used directly for the cathode electrode of water electrolysis hydrogen production Material, shows excellent electrocatalytic properties of hydrogen evolution：Tafel slopes are down to 30mV/dec, 10mA/cm2It is excessively electric under current density Position is~60mV, hence it is evident that better than the 10wt% business Pt/C catalyst under the conditions of.
In order to which the purpose of the present invention is better achieved, invention further provides a kind of flexibilities for water electrolysis hydrogen production The preparation method of nanoporous/amorphous composite material, the preparation method mainly include the following steps that：
1) amorphous alloy component of the selection with higher glass forming ability throws away method using melt and amorphous conjunction is prepared Golden strip or silk material；
2) alloying is taken off by surface and obtains nanoporous/amorphous composite structure.
Further, solution throws away the amorphous alloy ribbon or silk material that method is prepared in the preparation method step 1) Specific ingredient be NixZryTiz(Pt,Au,Pd)m, wherein 40≤x≤50,30≤y≤40,10≤z≤20,0≤m≤4, x+y + z+m=100, the ingredient are atomic percent.
Further, melt throws away Ni prepared by method in the step 1)xZryTiz(Pt,Au,Pd)mAmorphous alloy ribbon Thickness be 20~30 μm, width be 2~3mm, a diameter of 25~70 μm of amorphous alloy wire；The amorphous alloy ribbon or It is flexible that silk material all has good mechanical bend.
Further, the corrosive liquid that the de- alloying in surface uses in the step 2) is the HF of 0.025~0.1mol/L Solution, etching time are 1~4h.
Beneficial effects of the present invention are as follows：
(1) method that alloying is directly taken off using surface obtains controlling compound electric for nanoporous/amorphous of hydrolytic hydrogen production Pole material, preparation process is simple, is suitble to large-scale industrial production.
(2) nanoporous/amorphous being prepared controls composite material with good mechanical bend flexibility, can be directly used for The electrode material of electrochemistry liberation of hydrogen, without carrying out moditied processing.
(3) nanoporous/amorphous composite structure has both the co-continuous nanometer through-hole structure of high-specific surface area and amorphous closes Auri body, the synergistic effect of the two are conducive to obtain higher HER electro catalytic activities.
(4) flexible nano it is porous/amorphous composite structure can not only solve the porous electrocatalysis material of current block nanometer Generally existing brittleness and the problem of be not used to function element, traditional amorphous catalysis band specific surface can also be overcome not high and led The defects of performance of cause is insufficient has prodigious application potential in terms of high-performance electrolysis water hydrogen manufacturing electrode material.
Description of the drawings
Fig. 1 is Ni40Zr40Ti20-xPtxThe X-ray diffractogram of (x=0, x=1, x=2, x=3 and x=4) alloy thin band Spectrum.
Fig. 2 is Ni40Zr40Ti20Amorphous alloy wire surface takes off the surface Scanning Electron microscope photograph after alloying 1.5h.
Fig. 3 is Ni40Zr40Ti20Nanoporous/noncrystal substrate combination interface sweeps after the de- alloying in amorphous alloy wire surface Retouch electron microscope picture.
Fig. 4 is Ni40Zr40Ti20-xPtxAmorphous alloy wire surface takes off the surface Scanning Electron microscope figure after alloying 1.5h Piece：(a) x=1；(b) x=2；(c) x=3；(d) x=4.
Fig. 5 is Ni40Zr40Ti20Amorphous alloy wire surface takes off the front and back linear volt-ampere in 1mol/L KOH solutions of alloying Scan correlation curve.
Fig. 6 is that presoma is Ni40Zr40Ti20-xPtxThe nanometer of (x=1, x=2, x=3 and x=4) amorphous alloy ribbon is more Linear voltammetric scan correlation curve of the hole/amorphous combination electrode material in 1mol/L KOH electrolyte.
Fig. 7 is that presoma is Ni40Zr40Ti20-xPtxThe nanometer of (x=1, x=2, x=3 and x=4) amorphous alloy ribbon is more Hole/amorphous combination electrode material is in 0.5mol/L H2SO4Linear voltammetric scan correlation curve in electrolyte.
Specific implementation mode
With reference to the accompanying drawings and examples, technical scheme of the present invention will be described in further detail.
Embodiment 1：
With Ni40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) is used as presoma alloy nominal composition, will Required element carries out weighing proportioning, by pure element (Ni 99.99wt%, the Zr 99.99wt%, Pt needed for presoma alloy 99.99wt%), it is converted into quality (5g) according to the atomic percent of alloy to weigh up, then uses high-purity argon atmosphere vacuum arc The method of melting, melting obtain Ni40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) master alloy button ingot, melting 3~4 times, to ensure that master alloy ingot ingredient is uniform.
Equipment is got rid of using vacuum, by Ni40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) alloy pig sense Fusing should be heated, then molten metal liquid is slowly risen and is brought into contact with high-speed rotating water-cooled copper roller tip, metal Liquid is rapidly thrown away and is quickly cooled down, and Ni is prepared40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) is closed The diameter of spun gold, B alloy wire is controllable with copper roller rotating speed in 25~70 μ ms.
Embodiment 2：
With Ni40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) is used as presoma alloy nominal composition, will Required element carries out weighing proportioning, by pure element (Ni 99.99wt%, the Zr 99.99wt%, Pt needed for presoma alloy 99.99wt%), it is converted into quality (5g) according to the atomic percent of alloy to weigh up, then uses high-purity argon atmosphere vacuum arc The method of melting, melting obtain the Ni of different bullion contents40Zr40Ti20-xPtx(x=1, x=2, x=3 and x=4) master alloy Button ingot, melting 3~4 times, to ensure that master alloy ingot ingredient is uniform.
Carrying device is got rid of using vacuum, master alloy ingot is utilized into intermediate frequency power supply sensing heating refuse, is in pressure The high-purity argon gas effect of 0.2MPa or so is lower to be continuously quickly ejected into water cooling rotary copper roller, and Ni is prepared40Zr40Ti20-xPtx The thickness of (x=0, x=1, x=2, x=3 and x=4) alloy thin band, strip is 20~30 μm, and width is 2~3mm.
Fig. 1 show the Ni being prepared40Zr40Ti20-xPtx(x=0, x=1, x=2, x=3 and x=4) alloy thin band X ray diffracting spectrum, as a result show that melt throws away the Ni that method is prepared40Zr40Ti20-xPtxAlloy thin band is single Amorphous structure.
Embodiment 3：
With Ni40Zr40Ti20-xAux(x=1, x=2, x=3 and x=4) is used as presoma alloy nominal composition, by required member Element carries out weighing proportioning, by pure element (Ni 99.99wt%, the Zr 99.99wt%, Au needed for presoma alloy 99.99wt%), it is converted into quality (5g) according to the atomic percent of alloy to weigh up, then uses high-purity argon atmosphere vacuum arc The method of melting, melting obtain the Ni of different bullion contents40Zr40Ti20-xAux(x=1, x=2, x=3 and x=4) master alloy Button ingot, melting 3~4 times, to ensure that master alloy ingot ingredient is uniform.
Carrying device is got rid of using vacuum, master alloy ingot is utilized into intermediate frequency power supply sensing heating refuse, is in pressure The high-purity argon gas effect of 0.2MPa or so is lower to be continuously quickly ejected into water cooling rotary copper roller, and Ni is prepared40Zr40Ti20-xPtx The thickness of (x=1, x=2, x=3 and x=4) alloy thin band, strip is 20~30 μm, and width is 2~3mm.
Embodiment 4：
With Ni40Zr40Ti20-xPdx(x=1, x=2, x=3 and x=4) is used as presoma alloy nominal composition, by required member Element carries out weighing proportioning, by pure element (Ni 99.99wt%, the Zr 99.99wt%, Pd needed for presoma alloy 99.99wt%), it is converted into quality (5g) according to the atomic percent of alloy to weigh up, then uses high-purity argon atmosphere vacuum arc The method of melting, melting obtain the Ni of different bullion contents40Zr40Ti20-xPdx(x=1, x=2, x=3 and x=4) master alloy Button ingot, melting 3~4 times, to ensure that master alloy ingot ingredient is uniform.
Carrying device is got rid of using vacuum, master alloy ingot is utilized into intermediate frequency power supply sensing heating refuse, is in pressure The high-purity argon gas effect of 0.2MPa or so is lower to be continuously quickly ejected into water cooling rotary copper roller, and Ni is prepared40Zr40Ti20-xPdx The thickness of (x=1, x=2, x=3 and x=4) alloy thin band, strip is 20~30 μm, and width is 2~3mm.
Embodiment 5：
Using the Ni being prepared in embodiment 140Zr40Ti20Alloy amorphous B alloy wire is as presoma, 0.025mol/L HF aqueous solutions as corrosive liquid, carry out the de- alloying of chemistry, taken out after 1.5h, and use ultra-pure water and absolute alcohol multiple successively Cleaning removes residual chemicals in hole, nanoporous/amorphous composite wire material is prepared after dry.
Fig. 2 show Ni40Zr40Ti20Amorphous alloy wire surface takes off nanoporous/noncrystal substrate combination circle after alloying Face, it is observed that apparent layered structure, i.e. the nanoporous activated bimetallic layer on surface and the support of intermediate flexible amorphous Body.
Fig. 3 show Ni40Zr40Ti20Amorphous alloy wire surface takes off the surface topography after alloying 1.5h, it is observed that Its surface forms the nanometer through-hole structure of three-dimensional co-continuous, and aperture size is 5~10nm.
Embodiment 6：
Using the Ni being prepared in embodiment 240Zr40Ti20-xPtx(x=1, x=2, x=3 and x=4) amorphous alloy thin Band is used as presoma, the HF aqueous solutions of 0.025mol/L to carry out the de- alloying of chemistry as corrosive liquid, taken out after 1.5h, and according to It is secondary to be cleaned multiple times with ultra-pure water and absolute alcohol, residual chemicals in hole are removed, precious metals pt, which is prepared, after dry mixes Miscellaneous nanoporous/amorphous composite material strip.
Fig. 4 show Ni40Zr40Ti20-xPtx(x=1, x=2, x=3 and x=4) amorphous alloy ribbon takes off alloying 1.5h Surface topography afterwards, it is observed that its surface has been similarly formed the nanometer through-hole structure of three-dimensional co-continuous, internal aperture size Still it is 5~10nm, simultaneously because the addition of Pt, surface gradually forms similar cellular reticular structure.
Embodiment 7：
We are the Ni to be prepared in embodiment 1 respectively40Zr40Ti20Surface is de- in amorphous alloy wire and embodiment 5 closes Ni after aurification40Zr40Ti20For amorphous alloy wire as working electrode, platinum plate electrode is auxiliary electrode, and Ag/AgCl normal electrodes are Reference electrode constitutes three-electrode system, and linear voltammetric scan, sweep speed 50mV/s are carried out in 1mol/L KOH solutions.
Fig. 5 show polarization curve of the different composite electrode material after being converted into standard hydrogen electrode current potential, as a result shows Relative to pure amorphous alloy material, nanoporous/amorphous composite structure after the de- alloying in surface has clearly more powerful analysis Hydrogen catalysis activity.
Embodiment 8：
We are respectively with the Ni of difference Pt contents in embodiment 640Zr40Ti20-xPtx(x=1, x=2, x=3 and x=4) is non- Peritectic alloy strip surface takes off nanoporous/amorphous composite material for being prepared into of alloying as working electrode, supplemented by platinum plate electrode It is that reference electrode constitutes three-electrode system to help electrode, Ag/AgCl normal electrodes, and linear volt-ampere is carried out in 1mol/L KOH solutions Scanning, sweep speed 50mV/s.
Fig. 6 show polarization curve of the different composite electrode material after being converted into standard hydrogen electrode current potential, as a result shows After Pt is added, the Hydrogen Evolution Performance of nanoporous/amorphous composite material further strengthens, in 10mA/cm2Under current density Overpotential is 60mV, and Tafel slopes are also down to 30mV/dec, hence it is evident that is urged better than the 10wt% business Pt/C under same experimental conditions Agent.
Embodiment 9：
We are respectively with the Ni of difference Pt contents in embodiment 640Zr40Ti20-xPtx(x=1, x=2, x=3 and x=4) is non- Peritectic alloy strip surface takes off nanoporous/amorphous composite material for being prepared into of alloying as working electrode, supplemented by platinum plate electrode Electrode is helped, Ag/AgCl normal electrodes are that reference electrode constitutes three-electrode system, in 0.5mol/L H2SO4It is carried out in solution linear Voltammetric scan, sweep speed 50mV/s.
Fig. 7 show polarization curve of the different composite electrode material after being converted into standard hydrogen electrode current potential, as a result shows The nano composite structure equally shows excellent electrocatalytic hydrogen evolution performance in an acidic solution, and significant change does not occur for performance.
Using the flexible nano for preparing of the present invention it is porous/amorphous composite material is used directly for cathode hydrogen evolution electrode, show Excellent electrochemistry hydrogen evolution activity is shown, while also there is good cyclical stability have very in water electrolysis hydrogen production field Big application potential.

Claims (7)

1. a kind of flexible nano is porous/amorphous composite material, which is characterized in that the composite material by high-specific surface area doubly-linked Continuous nano porous layer and noncrystal substrate layer composition, form the nano composite structure of nanoporous active layer covering noncrystal substrate；Institute The nanoporous layer thickness of composite material is stated in 200~500nm ranges, internal aperture size is 5~10nm.
2. flexible nano according to claim 1 is porous/amorphous composite material, which is characterized in that the nanoporous/ Amorphous composite material keeps good mechanical flexibility, the arbitrary bending of 180 ° of energy, easily prepared flexible electrode device.
3. flexible nano according to claim 1 is porous/amorphous composite material, which is characterized in that the nanoporous/ Amorphous composite material can be directly used in the cathode electrode of water electrolysis hydrogen production, show excellent electrocatalytic properties of hydrogen evolution：Tafel is oblique Rate is down to 30mV/dec, 10mA/cm2Overpotential under current density is~60mV, hence it is evident that better than the 10wt% quotient under the conditions of Industry Pt/C catalyst.
4. a kind of flexible nano as described in claim 1-3 is porous/preparation method of amorphous composite material, which is characterized in that tool Preparation step is as follows：
1) amorphous alloy component of the selection with higher glass forming ability, throws away method using melt and amorphous alloy thin is prepared Band or silk material；
2) alloying is taken off by surface and obtains nanoporous/amorphous composite structure.
5. flexible nano according to claim 4 is porous/preparation method of amorphous composite material, which is characterized in that it is described The specific ingredient that solution throws away amorphous alloy ribbon or silk material that method is prepared in step 1) is NixZryTiz(Pt,Au,Pd )m, wherein 40≤x≤50,30≤y≤40,10≤z≤20,0≤m≤4, x+y+z+m=100, the ingredient is atomic percent Than.
6. flexible nano according to claim 4 is porous/preparation method of amorphous composite material, which is characterized in that it is described Melt throws away the Ni of method preparation in step 1)xZryTiz(Pt,Au,Pd)mThe thickness of amorphous alloy ribbon is 20~30 μm, width For 2~3mm, a diameter of 25~70 μm of amorphous alloy wire；The amorphous alloy ribbon or silk material all has good machinery Bending is flexible.
7. flexible nano according to claim 4 is porous/preparation method of amorphous composite material, which is characterized in that it is described For the corrosive liquid that the de- alloying in surface uses in step 2) for the HF solution of 0.025~0.1mol/L, etching time is 1~4h.
CN201810416430.XA 2018-05-03 2018-05-03 A kind of flexible nano is porous/amorphous composite material and preparation method thereof Pending CN108707922A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109706409A (en) * 2019-01-21 2019-05-03 河北工业大学 A kind of nano-meter porous amorphous alloy and preparation method thereof
CN110055477A (en) * 2019-03-04 2019-07-26 天津大学 A kind of nanoporous ni-based amorphous alloy material and its application in water electrolysis hydrogen production
CN110923752A (en) * 2019-10-29 2020-03-27 东北大学 Transition metal powder with high specific surface area and preparation method thereof
CN112657505A (en) * 2019-09-30 2021-04-16 中国科学院物理研究所 Catalytic material for catalyzing water electrolysis hydrogen evolution reaction under acidic condition, preparation method and application thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760706A (en) * 2008-12-24 2010-06-30 中国科学院金属研究所 Aluminum-based micro/nano-meter porous amorphous alloy material and preparation method thereof
CN105261491A (en) * 2015-11-23 2016-01-20 河北工业大学 Preparation method of flexible nano porous nickel/nickel oxide composite electrode plate
CN105648478A (en) * 2016-01-13 2016-06-08 大连理工大学 Preparation method of magnetic nano porous Fe-Pt alloy with electro-oxidation catalytic performance
CN106222584A (en) * 2016-08-26 2016-12-14 北京航空航天大学 A kind of nanoporous Fe base noncrystal alloy and preparation method and the application on analysis oxygen catalysis electrode
CN107240507A (en) * 2017-07-18 2017-10-10 河北工业大学 A kind of nanoporous nickel nickel electrode material for super capacitor and preparation method thereof
CN107338402A (en) * 2017-07-18 2017-11-10 河北工业大学 A kind of nanoporous copper-silver bimetallic/bimetallic oxide and its preparation method and application
CN107385362A (en) * 2017-07-10 2017-11-24 上海理工大学 A kind of cu-base amorphous alloy silk with high-intensity high-tenacity and preparation method thereof
CN107419128A (en) * 2017-06-22 2017-12-01 北京航空航天大学 A kind of preparation method of three-dimensional communication nano porous metal and its application on electrolysis water cathode catalysis material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760706A (en) * 2008-12-24 2010-06-30 中国科学院金属研究所 Aluminum-based micro/nano-meter porous amorphous alloy material and preparation method thereof
CN105261491A (en) * 2015-11-23 2016-01-20 河北工业大学 Preparation method of flexible nano porous nickel/nickel oxide composite electrode plate
CN105648478A (en) * 2016-01-13 2016-06-08 大连理工大学 Preparation method of magnetic nano porous Fe-Pt alloy with electro-oxidation catalytic performance
CN106222584A (en) * 2016-08-26 2016-12-14 北京航空航天大学 A kind of nanoporous Fe base noncrystal alloy and preparation method and the application on analysis oxygen catalysis electrode
CN107419128A (en) * 2017-06-22 2017-12-01 北京航空航天大学 A kind of preparation method of three-dimensional communication nano porous metal and its application on electrolysis water cathode catalysis material
CN107385362A (en) * 2017-07-10 2017-11-24 上海理工大学 A kind of cu-base amorphous alloy silk with high-intensity high-tenacity and preparation method thereof
CN107240507A (en) * 2017-07-18 2017-10-10 河北工业大学 A kind of nanoporous nickel nickel electrode material for super capacitor and preparation method thereof
CN107338402A (en) * 2017-07-18 2017-11-10 河北工业大学 A kind of nanoporous copper-silver bimetallic/bimetallic oxide and its preparation method and application

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CN109706409A (en) * 2019-01-21 2019-05-03 河北工业大学 A kind of nano-meter porous amorphous alloy and preparation method thereof
CN110055477A (en) * 2019-03-04 2019-07-26 天津大学 A kind of nanoporous ni-based amorphous alloy material and its application in water electrolysis hydrogen production
CN112657505A (en) * 2019-09-30 2021-04-16 中国科学院物理研究所 Catalytic material for catalyzing water electrolysis hydrogen evolution reaction under acidic condition, preparation method and application thereof
CN110923752A (en) * 2019-10-29 2020-03-27 东北大学 Transition metal powder with high specific surface area and preparation method thereof

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Application publication date: 20181026