CN106609346B - A kind of amorphous alloy and its preparation method and application - Google Patents
A kind of amorphous alloy and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to catalyst field, a kind of amorphous alloy and its preparation method and application is disclosed.The chemical formula of the amorphous alloy is MxAyPz, wherein M is Pd and/or Pt；A is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo or a variety of；X, y and z is molar fraction, and 1≤x≤60,1≤y≤60,1≤z≤40, x+y+z=100.Amorphous alloy provided by the invention can be used as the catalyst in evolving hydrogen reaction, have the advantages that catalytic activity height and stability are good in acid system.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of amorphous alloy and its preparation method and application.
Background technique
Renewable energy (such as solar energy, wind energy, water potential) as media storage, transport and is converted into achievable ring using hydrogen
Border close friend and social sustainable development.Current 95% or more hydrogen is from fossil fuel, and important sources of the water as hydrogen
One of, the gross energy of the hydrogen extracted from it is 9000 times of earth fossil fuel heat amount.It is urged by evolving hydrogen reaction (HER) electricity
Changing splitting water is the important process with high energy conversion efficiency.Currently, existing evolving hydrogen reaction catalyst is main
Based on noble metals such as platinum, but the limited reserves of platinum and high cost prevent the business application of this technology.MoS2, Mo2C,
MoB, MoP, MoSe2, WS2The Pt base catalyst replaced is studied as with 3d transition metal.In recent years, 3d transition metal, example
Such as, Fe, Co, Ni and its derivative as the substitution of Pt base catalyst cause great pass due to high abundance and low cost
Note, but these metals are easy to be corroded in acidic electrolysis system.For acid system evolving hydrogen reaction (HER), replace expensive
The significant challenge that metal-based catalyst faces is the stability of the low efficiency of non-precious metal catalyst and difference.
Summary of the invention
The problem that present invention aim to address the catalyst activities of evolving hydrogen reaction in acid system is low, stability is poor, mentions
For a kind of amorphous alloy and its preparation method and application.
To achieve the goals above, the present invention provides a kind of amorphous alloys, wherein the chemical formula of the amorphous alloy is
MxAyPz；
Wherein, M is Pd and/or Pt；A is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo or a variety of；
X, y and z is molar fraction, and 1≤x≤60,1≤y≤60,1≤z≤40, x+y+z=100.
The present invention also provides a kind of methods for preparing the amorphous alloy, wherein this approach includes the following steps：
(1) metal M and metal A is subjected to melting, obtains MA master alloy ingot；
(2) the MA master alloy ingot and phosphorus are subjected to induction melting, obtain MAP master alloy；And
(3) the MAP master alloy and diboron trioxide are subjected to induction heating processing, then cooled down.
Furthermore the present invention also provides the amorphous alloys prepared by the above method.
In addition, the present invention also provides the amorphous alloys to apply in evolving hydrogen reaction.
Amorphous alloy provided by the invention can be used as the catalyst in evolving hydrogen reaction, in acid system there is catalysis to live
Property height and the good advantage of stability.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the evolving hydrogen reaction polarization curve of embodiment 1 and comparative example 1；
Fig. 2 is the Tafel curve figure of embodiment 1 and comparative example 1；
Fig. 3 is the polarization curve after the different cycle-indexes of embodiment 1；
Fig. 4 is the chronoa mperometric plot figure of embodiment 1 and comparative example 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of amorphous alloys, wherein the chemical formula of the amorphous alloy is MxAyPz；
Wherein, M is Pd and/or Pt, preferably Pd；A is one in Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo
Kind is a variety of；
Preferably, one of A Fe, Co, Ni, Cu and Zn or a variety of, preferably in Fe, Co, Ni, Cu and Zn at least
Two kinds, more preferably Cu with selected from the combination of at least one of Fe, Co and Ni, the combination of most preferably Cu and Ni.
In a preferred embodiment, M Pd, A are the combination of Cu and Ni.
In the present invention, x, y and z are molar fraction, and 1≤x≤60,1≤y≤60,1≤z≤40, x+y+z=100；
Preferably, 25≤x≤50,25≤y≤50,10≤z≤30；It is highly preferred that 35≤x≤45,35≤y≤45,15≤z≤25；
In most preferred situation, x=40, y=40, z=20.
In the present invention, the structure of the amorphous alloy is not particularly limited, can be structure conventional in the art,
Such as band, film, mesoporous material, one-dimensional nano line array or 1-dimention nano pipe array, preferably band or film, more preferably
For band.
The present invention also provides a kind of methods for preparing the amorphous alloy, wherein this approach includes the following steps：
(1) metal M and metal A is subjected to melting, obtains MA master alloy ingot；
(2) the MA master alloy ingot and phosphorus are subjected to induction melting, obtain MAP master alloy；And
(3) the MAP master alloy and diboron trioxide are subjected to induction heating processing, then cooled down.
The fusion process of a preferred embodiment of the invention, step (1) includes：It will first be melted with mechanical pump
It is 10Pa or less (such as 8Pa, 5Pa, 3Pa, 1Pa or 0.5Pa) that refining room, which is evacuated to vacuum degree, then is taken out working chamber very with molecular pump
Sky is to 3 × 10-3Pa or less (such as 3 × 10-3Pa、1×10-3Pa、7×10-4Pa、3×10-4Pa、5×10-6Pa or 1 × 10-7Pa),
Then it is filled with inert gas, raw metal M and metal A is then made to carry out melting in the working chamber.The fusion process can
To implement in arc-melting furnace.The arc-melting furnace can use tungsten electrode.
A preferred embodiment of the invention, in order to adsorb the indoor oxygen of melting and other impurities, step (1)
The fusion process it is also preferable to include：Before injecting raw metal M and metal A and after being filled with inert gas, injection
Titanium sponge carries out melting.
In the present invention, to the dosage of titanium sponge, there is no particular limitation, if the dosage of titanium sponge can adsorb completely it is molten
Refine indoor oxygen and other impurities.Under preferable case, with the total weight of the dosage of raw metal M and metal A for 100 weights
Part meter is measured, the dosage of the titanium sponge is 10-20 parts by weight, more preferably 14-16 parts by weight.
In the present invention, in order to guarantee that melting is uniform, the fusion process of step (1) can repeat implementation 2-7 times, preferably
It is 3-5 times.
In the present invention, during the induction melting of step (2), since phosphorus is volatile, under preferable case, the use of phosphorus
Amount is 1.01-1.7 times, preferably 1.1-1.4 times of theoretical molar equivalent.
In the present invention, the induction melting process of step (2) can under vacuum conditions, it is real in quartz glass tube
It applies；Preferably, the vacuum degree of the vacuum condition is 2 × 10-3-4×10-3Pa。
In step (2), after the induction melting process, the quality of obtained MAP master alloy is weighed, is led to
The quality for crossing the MAP master alloy subtracts the quality of the MA master alloy ingot to obtain the phosphorous matter of reality of the MAP master alloy
Amount.If the quality of phosphorus is higher, a certain amount of MA master alloy ingot is added according still further to proportion and continues induction and is melted
Refining, until obtaining the MAP master alloy of suitable phosphorus content.
It is not special to the dosage of the diboron trioxide in the induction heating processing of step (3) in the present invention
Restriction, still, in order to improve the Forming ability of amorphous glass, under preferable case, the diboron trioxide and mother MAP are closed
The volume ratio of the dosage of gold is 1.5-2.5：1, more preferably 1.5-2.3：1, further preferably 1.6-2：1.
In the present invention, the process of the induction heating processing of step (3) may include：By the MAP master alloy and three
It aoxidizes two boron to be put into quartz ampoule, quartz ampoule is evacuated to 10-5Pa or less (such as 10-6Pa、10-7Pa、10-8Pa or 10-9Pa),
It is filled with inert gas and seals, then the quartz ampoule of sealing is carried out to induction heating processing in high vacuum single roller strip furnace.This
The high vacuum at place refers to that vacuum degree is 6 × 10-4Pa or less.
In the present invention, the method can also include：The MAP master alloy obtained after step (3) processing is heated to melting,
Then it is ejected on matrix, to obtain amorphous alloy strip.Wherein, the heating process can be real in such a way that this field is conventional
It applies, such as can be heated for induced current.
In a preferred embodiment of the invention, the MAP master alloy is placed in quartz ampoule, by the quartz
Pipe is placed in the induction coil of high vacuum single roller strip furnace, and adjustment quartz ampoule height makes the distance between its nozzle and copper roller be 2-
Vacuum degree in the spun furnace is evacuated to 4 × 10 by 3mm-4Pa or less (such as 1 × 10-4Pa、4×10-5Pa、3×10-6Pa or 1 ×
10-7Pa), the pressure being filled in high-purity argon gas (purity >=99.999%) to the spun furnace is 0.05-0.08MPa, using sense
It answers electric current to heat the MAP master alloy to molten condition, is injected on the copper roller of rotation, to obtain amorphous alloy strip.Its
In, the revolving speed of the copper roller is 10-50m/s.
In the present invention, the vacuum degree refers to absolute vacuum degree.
Furthermore the present invention also provides a kind of amorphous alloys prepared by the method for the invention.
In addition, the present invention also provides the amorphous alloys to apply in evolving hydrogen reaction.Amorphous alloy provided by the invention
It can be used as the catalyst in evolving hydrogen reaction, there is high catalytic activity and stability in acid system.
The present invention will be described in detail by way of examples below.In following embodiment, the electrochemistry of amorphous alloy strip
Test method is as follows：
(1) to the pretreatment of amorphous alloy strip.With sand paper polishing amorphous alloy belt surface removal impurity and oxidation film, use
0.5mol/L sulfuric acid and deionized water alternately washing five times, then alternately washed five times with 1mol/LKOH solution and deionized water, it does
It is spare after dry；
(2) electro-chemical test.Catalytic activity and stability characterization are carried out using typical three electrode tests system.Take area
For 0.5cm2The step of (1) processed amorphous alloy strip as working electrode, area 1cm2Pt piece be used as to electrode, Ag/
AgCl electrode as reference electrode (potential expression way be E vs RHE=E vs Ag/AgCl+0.059 × pH+0.204V,
RHE is reversible hydrogen reference electrode).Electrolyte is 0.5mol/L sulfuric acid.Before test, first by working electrode in 0.5mol/L sulfuric acid
In solution, with the scanning speed of 100mV/s, voltage range is in 0-1.2V vs RHE, using cyclic voltammetric (CV) method activation 10
Circle, with activated electrode and removal adsorption impurity.
The test of evolving hydrogen reaction catalytic activity：Using linear scan (LSV) method, scanning speed 2mV/s, voltage range is
0.1V-–0.6V vs RHE。
Evolving hydrogen reaction stability test：Using two methods of cyclic voltammetric (CV) method and chrono-amperometric (CA) method.CA test
Using three-electrode system as above, test voltage is 0.3V vs RHE, testing time 50000s；CV test condition is voltage model
It encloses for 0.1V- -0.3V vs RHE, scanning speed 100mV/s, takes 1000 circles respectively, catalyst test its line after 10000 circles
Property scanning polarization curve.
In following embodiment, Pd, Pt, Cu, Ni, P, Co and Fe have purchased from Beijing Cui Bolin non-ferrous metal technology development center
Limit company；In comparative example, 10wt%Pt/C material is purchased from AlfaAesar (China) Chemical Co., Ltd..
Embodiment 1
The present embodiment is for illustrating amorphous alloy Pd40Cu30Ni10P20Preparation method.
Pd, Cu, Ni by purity greater than 99.9% is according to 40：30：10 ratio mixing, gross mass are 20 grams.First use machine
Arc melting room vacuum degree is evacuated to 10Pa by tool pump, then is evacuated to 1x10 with molecular pump-3Pa is then charged with high-purity argon gas, by 2g
Titanium sponge is put into working chamber and carries out melting, then the mixture of Pd, Cu and Ni are put into melting 3 times in electric arc furnaces, obtains PdCuNi
Master alloy ingot.
The quality for weighing obtained PdCuNi master alloy ingot, according to Pd40Cu30Ni10P20Phosphorus needed for composition proportion calculates
Quality weighs the phosphorus that quality is 1.2 times of theoretical values, and it is 2 × 10 that vacuum degree is sealed in together with PdNiCu master alloy ingot-3The stone of Pa
Induction melting is carried out in English glass tube, obtains Pd40Cu30Ni10P20Master alloy.
By Pd obtained above40Cu30Ni10P20Master alloy and volume are Pd40Cu30Ni10P202 times of master alloy of three oxidations
Two boron are put into togerther quartz ampoule, are evacuated to 10-5Pa is filled with the quartzy seal of tube after high-purity argon gas, the quartz ampoule of sealing is existed
Induction heating is handled in vacuum list roller spun furnace, takes out Pd after cooling40Cu30Ni10P20Alloy.
By Pd40Cu30Ni10P20Alloy is put into quartz ampoule, is placed in spun furnace induction coil, and quartz ampoule height is adjusted
Make distance 2mm between its nozzle and copper roller, vacuum degree in spun furnace is evacuated to 4x10-4Pa is filled with high-purity argon gas to furnace internal pressure
By force it is 0.06MPa, Pd is heated using induced current40Cu30Ni10P20To molten condition, be then injected into revolving speed is alloy
On the copper roller of 10m/s to get arrive Pd40Cu30Ni10P20Amorphous alloy strip.
The Pd tested using electro-chemical test method40Cu30Ni10P20Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, catalytic activity result is as shown in table 1 and Fig. 1-2, and stability result is as shown in table 1 and Fig. 3-4.
Comparative example 1
This comparative example is used to illustrate catalytic activity and stability of the 10wt%Pt/C material in Electrocatalytic Activity for Hydrogen Evolution Reaction reaction.
Catalytic activity and stability of the commodity 10wt%Pt/C material in evolving hydrogen reaction are tested using electro-chemical test method,
Catalytic activity result is as shown in table 1 and Fig. 1-2, and stability result is as shown in table 1 and Fig. 4.
Embodiment 2
The present embodiment is for illustrating amorphous alloy Pd35Cu25Ni20P20Preparation method.
Pd, Cu, Ni by purity greater than 99.9% is according to 35：25：20 ratio mixing, gross mass are 20 grams.First use machine
Arc melting room vacuum degree is evacuated to 8Pa by tool pump, then is evacuated to 3x10 with molecular pump-3Pa is then charged with high-purity argon gas, by the sea 4g
Continuous titanium is put into working chamber and carries out melting, then the mixture of Pd, Cu and Ni are put into melting 5 times in electric arc furnaces, obtains PdCuNi mother
Alloy pig.
The quality for weighing obtained PdCuNi master alloy ingot, according to Pd35Cu25Ni20P20Phosphorus needed for composition proportion calculates
Quality weighs the phosphorus that quality is 1.4 times of theoretical values, and it is 4 × 10 that vacuum degree is sealed in together with PdNiCu master alloy ingot-3The stone of Pa
Induction melting is carried out in English glass tube, obtains Pd35Cu25Ni20P20Master alloy.
By Pd obtained above35Cu25Ni20P20Master alloy and volume are Pd35Cu25Ni20P201.6 times of master alloy of three oxygen
Change two boron and be put into togerther quartz ampoule, is evacuated to 10-6Pa is filled with after high-purity argon gas by the quartzy seal of tube, by the quartz ampoule of sealing
Induction heating is handled in vacuum list roller spun furnace, takes out Pd after cooling35Cu25Ni20P20Alloy.
By Pd35Cu25Ni20P20Alloy is put into quartz ampoule, is placed in spun furnace induction coil, and quartz ampoule height is adjusted
Make distance 3mm between its nozzle and copper roller, vacuum degree in spun furnace is evacuated to 1x10-4Pa is filled with pressure in high-purity argon gas to furnace
For 0.08MPa, Pd is heated using induced current35Cu25Ni20P20For alloy to molten condition, being then injected into revolving speed is 50m/
On the copper roller of s to get arrive Pd35Cu25Ni20P20Amorphous alloy strip.
The Pd tested using electro-chemical test method35Cu25Ni20P20Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, the results are shown in Table 1.
Embodiment 3
The present embodiment is for illustrating amorphous alloy Pd40Cu20Ni15P25Preparation method.
Pd, Cu, Ni by purity greater than 99.9% is according to 40：20：15 ratio mixing, gross mass are 20 grams.First use machine
Arc melting room vacuum degree is evacuated to 5Pa by tool pump, then is evacuated to 3x10 with molecular pump-4Pa is then charged with high-purity argon gas, by the sea 4g
Continuous titanium is put into working chamber and carries out melting, then the mixture of Pd, Cu and Ni are put into melting 4 times in electric arc furnaces, obtains PdCuNi mother
Alloy pig.
The quality for weighing obtained PdCuNi master alloy ingot, according to Pd40Cu20Ni15P25Phosphorus needed for composition proportion calculates
Quality weighs the phosphorus that quality is 1.1 times of theoretical values, and it is 3 × 10 that vacuum degree is sealed in together with PdNiCu master alloy ingot-3The stone of Pa
Induction melting is carried out in English glass tube, obtains Pd40Cu20Ni15P25Master alloy.
By Pd obtained above40Cu20Ni15P25Master alloy and volume are Pd40Cu20Ni15P251.8 times of master alloy of three oxygen
Change two boron and be put into togerther quartz ampoule, is evacuated to 10-5Pa is filled with after high-purity argon gas by the quartzy seal of tube, by the quartz ampoule of sealing
Induction heating is handled in vacuum list roller spun furnace, takes out Pd after cooling40Cu20Ni15P25Alloy.
By Pd40Cu20Ni15P25Alloy is put into quartz ampoule, is placed in spun furnace induction coil, and quartz ampoule height is adjusted
Make distance 2mm between its nozzle and copper roller, vacuum degree in spun furnace is evacuated to 4x10-5Pa is filled with pressure in high-purity argon gas to furnace
For 0.05MPa, Pd is heated using induced current40Cu20Ni15P25For alloy to molten condition, being then injected into revolving speed is 30m/
On the copper roller of s to get arrive Pd40Cu20Ni15P25Amorphous alloy strip.
The Pd tested using electro-chemical test method40Cu20Ni15P25Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, the results are shown in Table 1.
Embodiment 4
The present embodiment is for illustrating amorphous alloy Pd40Co30Fe10P20Preparation method.
Pd is prepared according to the method for embodiment 140Cu30Fe10P20, unlike, purity is greater than to 99.9% Pd, Co, Fe
According to 40：30：10 ratio mixing, gross mass are 20 grams.
The Pd tested using electro-chemical test method40Cu30Fe10P20Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, the results are shown in Table 1.
Embodiment 5
The present embodiment is for illustrating amorphous alloy Pd35Co25Fe20P20Preparation method.
Pd is prepared according to the method for embodiment 235Co25Fe20P20, unlike, purity is greater than to 99.9% Pd, Co, Fe
According to 35：25：20 ratio mixing, gross mass are 20 grams.
The Pd tested using electro-chemical test method35Co25Fe20P20Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, the results are shown in Table 1.
Embodiment 6
The present embodiment is for illustrating amorphous alloy Pd40Co20Fe15P25Preparation method.
Pd is prepared according to the method for embodiment 340Co20Fe15P25, unlike, purity is greater than to 99.9% Pd, Co, Fe
According to 40：20：15 ratio mixing, gross mass are 20 grams.
The Pd tested using electro-chemical test method40Co20Fe15P25Catalysis of the amorphous alloy strip in evolving hydrogen reaction is living
Property and stability, the results are shown in Table 1.
Embodiment 7
The present embodiment is for illustrating amorphous alloy Pt40Cu40P20Preparation method.
Pt is prepared according to the method for embodiment 140Cu40P20, unlike, Pt, Cu by purity greater than 99.9% are according to 1：
1 ratio mixing, gross mass are 20 grams.
The Pt tested using electro-chemical test method40Cu40P20Catalytic activity of the amorphous alloy strip in evolving hydrogen reaction and
Stability, the results are shown in Table 1.
Embodiment 8
The present embodiment is for illustrating amorphous alloy Pt35Cu45P20Preparation method.
Pt is prepared according to the method for embodiment 235Cu45P20, unlike, by purity greater than 99.9% Pt, Cu according to
35：45 ratio mixing, gross mass are 20 grams.
The Pt tested using electro-chemical test method35Cu45P20Catalytic activity of the amorphous alloy strip in evolving hydrogen reaction and
Stability, the results are shown in Table 1.
Embodiment 9
The present embodiment is for illustrating amorphous alloy Pt40Cu35P25Preparation method.
Pt is prepared according to the method for embodiment 340Cu35P25, unlike, by purity greater than 99.9% Pt, Cu according to
40：35 ratio mixing, gross mass are 20 grams.
The Pt tested using electro-chemical test method40Cu35P25Catalytic activity of the amorphous alloy strip in evolving hydrogen reaction and
Stability, the results are shown in Table 1.
Table 1
Note：Current density/test initial current density after test in 50000 seconds after electric current conservation rate=test 50000 seconds.
Can be seen that amorphous alloy provided by the invention in current density from the data in Fig. 1-2 and table 1 is -1.0mA/
cm2It is suitable with business Pt/C catalyst to locate corresponding voltage and Tafel slope, electric current with higher after test in 50000 seconds
Conservation rate, also, from Fig. 3-4 as can be seen that using the cyclic voltammetry curve after 1000 circle of cyclic voltammetry scanning and 10000 circles
There is no vary widely.Therefore amorphous alloy provided by the invention has high catalytic activity and stabilization in evolving hydrogen reaction
Property.The present invention solves the problems, such as that the catalyst activity of evolving hydrogen reaction in acid system is low, stability is poor.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of amorphous alloy, which is characterized in that the chemical formula of the amorphous alloy is MxAyPz；
Wherein, M is Pd and/or Pt；A is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo or a variety of；
X, y and z is molar fraction, and 35≤x<45,35≤y≤45,15≤z≤25, x+y+z=100.
2. amorphous alloy according to claim 1, wherein M Pd.
3. amorphous alloy according to claim 1 or 2, wherein one of A Fe, Co, Ni, Cu and Zn or a variety of.
4. amorphous alloy according to claim 3, wherein at least two in A Fe, Co, Ni, Cu and Zn.
5. amorphous alloy according to claim 4, wherein A is Cu and the group selected from least one of Fe, Co and Ni
It closes.
6. amorphous alloy according to claim 5, wherein A is the combination of Cu and Ni.
7. according to claim 1, amorphous alloy described in any one of 2 and 4-6, wherein the structure of the amorphous alloy is
Band, film, mesoporous material, one-dimensional nano line array or 1-dimention nano pipe array.
8. a kind of method for preparing amorphous alloy described in any one of claim 1-7, wherein this method includes following step
Suddenly：
(1) metal M and metal A is subjected to melting, obtains MA master alloy ingot；
(2) the MA master alloy ingot and phosphorus are subjected to induction melting, obtain MAP master alloy；And
(3) the MAP master alloy and diboron trioxide are subjected to induction heating processing, then cooled down.
9. according to the method described in claim 8, wherein, the fusion process of step (1) repeats to implement 2-7 times.
10. according to the method described in claim 9, wherein, the fusion process of step (1) repeats to implement 3-5 times.
11. according to the method described in claim 8, wherein, during the induction melting of step (2), the dosage of phosphorus is
1.01-1.7 times of theoretical molar equivalent.
12. according to the method for claim 11, wherein during the induction melting of step (2), the dosage of phosphorus is
1.1-1.4 times of theoretical molar equivalent.
13. the method according to any one of claim 8,11 and 12, wherein the induction melting mistake of step (2)
Journey is implemented under vacuum conditions, in quartz glass tube.
14. according to the method for claim 13, wherein the vacuum degree of the vacuum condition is 2 × 10-3-4×10-3Pa。
15. according to the method described in claim 8, wherein, in the induction heating processing of step (3), described three are aoxidized
The volume ratio of the dosage of two boron and the MAP master alloy is 1.5-2.5：1.
16. the method according to claim 8 or 15, wherein the process of the induction heating of step (3) processing includes：
The MAP master alloy and diboron trioxide are put into quartz ampoule, quartz ampoule is evacuated to 10-5Pa is hereinafter, be filled with indifferent gas
Body simultaneously seals, then the quartz ampoule of sealing is carried out to induction heating processing in high vacuum single roller strip furnace.
17. the method according to any one of claim 8-12,14 and 15, wherein the method also includes：By step
(3) the MAP master alloy obtained after handling is heated to melting, and is then ejected on matrix, to obtain amorphous alloy strip.
18. the amorphous alloy of the preparation of the method as described in any one of claim 8-17.
19. amorphous alloy described in any one of claim 1-7 and 18 is applied in evolving hydrogen reaction.
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| CN110952110A (en) * | 2018-09-27 | 2020-04-03 | 天津大学 | Nano-porous Pd-Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis |
| CN109680224B (en) * | 2019-01-16 | 2021-05-04 | 南京理工大学 | Preparation method of nano porous palladium-based amorphous alloy |
| US11339486B2 (en) * | 2019-03-11 | 2022-05-24 | The University Of Akron | Porous amorphous metallic electrocatalytic materials for water electrolysis |
| CN109881028A (en) * | 2019-04-11 | 2019-06-14 | 福建工程学院 | A kind of resistant amorphous alloy system and its application |
| CN110257733B (en) * | 2019-07-31 | 2020-06-30 | 燕山大学 | Ni-Pd-P amorphous alloy nanowire and preparation method thereof |
| CN111041519A (en) * | 2019-11-21 | 2020-04-21 | 中国科学院金属研究所 | Non-noble metal amorphous electrolyzed water anode material and in-situ growth preparation method |
| CN111485249B (en) * | 2020-04-30 | 2021-02-09 | 东南大学 | Method for improving catalytic hydrogen evolution performance of iron-based amorphous alloy |
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