CN107419128A - A kind of preparation method of three-dimensional communication nano porous metal and its application on electrolysis water cathode catalysis material - Google Patents

A kind of preparation method of three-dimensional communication nano porous metal and its application on electrolysis water cathode catalysis material Download PDF

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CN107419128A
CN107419128A CN201710478958.5A CN201710478958A CN107419128A CN 107419128 A CN107419128 A CN 107419128A CN 201710478958 A CN201710478958 A CN 201710478958A CN 107419128 A CN107419128 A CN 107419128A
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dimensional communication
porous metal
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CN107419128B (en
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张涛
左磊
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Beihang University
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Abstract

The invention discloses a kind of preparation method of three-dimensional communication nano porous metal and its application on electrolysis water cathode catalysis material.This three-dimensional communication nano porous metal is with MgxMyNzNon-crystaline amorphous metal is presoma, removes what the element in alloy beyond Cu, Ni, Pd, Pt, Au and Ag obtained by the method for the removal alloying in weakly acidic ammonium salt solution.Removal alloying process can be carried out under ultrasound or without ultrasonic environment.The MgxMyNzIn non-crystaline amorphous metal presoma, the one or more in M Cu, Ni, Pd, Pt, Au and Ag, N is the one or more in lanthanide series similar in physicochemical properties.The three-dimensional communication nano porous metal of preparation has very high specific surface area, and its specific surface area reaches 63.8m2/g.The three-dimensional communication nano porous metal of preparation shows excellent catalytic activity of hydrogen evolution.

Description

A kind of preparation method of three-dimensional communication nano porous metal and its urged in electrolysis water negative electrode Change the application on material
Technical field
The method of three-dimensional communication nano porous metal is prepared and its in electricity by removal alloying method the present invention relates to a kind of Solve the application on water cathode catalysis material.
Background technology
Nano porous metal has a wide range of applications in fields such as sensor, catalysis, acoustics and energy stores.And remove alloy Change is a kind of very convenient, effective method for preparing nano porous metal.It is by optionally eroding in alloy One or more constituent elements, remaining constituent element spontaneously form nano-porous structure.Many metals such as platinum, palladium, gold, silver, copper and mickel etc. Metal can be prepared by the method for removal alloying.For prepare nano porous metal presoma alloy selection for more Pore structure important.The structure of non-crystaline amorphous metal, composition are uniform, the fault of construction such as dislocation-free, crystal boundary, are removal alloying methods Prepare the preferable persursor material of nano porous metal.In order to increase the specific surface area of nano porous metal, acquisition is often required that Finer frenulum, aperture structure.And for some applications, such as the cathode catalysis material of electrolyzed alkaline water, it is desirable to presoma group First energy structure is stabilized in alkaline solution to realize certain catalytic stability.Therefore, one aspect of the present invention enables to make Standby nano porous metal possesses bigger specific surface area, on the other hand it is also possible that the nano porous metal nickel/platinum prepared Available for electrolyzed alkaline water cathode catalysis material and there is certain stability.
The content of the invention
One of the object of the invention be to provide it is a kind of three-dimensional communication nano porous metal is prepared by removal alloying method before Drive body and corresponding etchant solution.Presoma is MgxMyNzNon-crystaline amorphous metal, wherein M are one kind in Cu, Ni, Pd, Pt, Au and Ag Or more than one, N be lanthanide series similar in physicochemical properties in one or more, the MgxMyNzNon-crystaline amorphous metal Middle atomic percentage x+y+z=100,40≤x≤90,5≤y≤40,5≤z≤40.
Lanthanide series refers to La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Etchant solution is ammonium salt solution, and the anion in ammonium salt is strong acid radical ion, and the strong acid radical ion refers to (NH4)2SO4, NH4Cl, NH4NO3, NH4F, NH4Br, NH4Cl, NH4I, NH4MnO4And NH4ClO4。
The second object of the present invention is to provide a kind of powder for obtaining and having three-dimensional communication nano-porous structure.Three-dimensional communication The ultrasound that is obtained by introducing of nanoporous powder is realized with accelerated stress corrosion process.
The three of the object of the invention be to provide it is a kind of for electrolysis water cathode catalysis material have high catalytic activity, stability Electrode material.Making step includes：By the three-dimensional communication nano porous metal of preparation and polytetrafluoroethylene (PTFE) and acetylene black according to Certain ratio is mixed, ground, and is ground to well mixed, obtains thick slurry, can be added in mixed process certain The ethanol of amount plays a part of dilution, takes a certain amount of slurry, and it is uniformly applied in nickel foam, obtains carrying active thing The nickel foam of matter；The nickel foam of carrying active material is placed on after drying more than the 5min times in 40 DEG C of temperatures above baking ovens and taken Go out, be placed on tablet press machine under 1Mpa pressure above and carry out tabletting；Nickel foam after compacting is positioned over 40 DEG C of temperatures above Continue to dry more than 1h in baking oven, then take out, obtain three-dimensional communication nano porous metal electrolysis water cathode hydrogen evolution electrode.
Presoma alloy has the defects of amorphous structure, no crystal boundary, dislocation, and base is laid to prepare uniform loose structure Plinth.
The frenulum size ＜ 10nm of the three-dimensional communication nano porous metal of preparation, aperture ＜ 10nm, specific surface area are reachable 63.8m2/g。
Brief description of the drawings
Fig. 1 is Mg59Ni25La16X ray diffracting spectrum before and after alloy corrosion, show that presoma is amorphous state knot before corroding Structure, the crystal peak occurred after corrosion correspond to face-centered cubic nickel.
Fig. 2 is with Mg59Ni25La16Non-crystaline amorphous metal is that the scanning of three-dimensional communication nanoporous nickel particle prepared by presoma is shone Piece.
Fig. 3 is with Mg65Ni25La16Non-crystaline amorphous metal is sweeping for three-dimensional communication nanoporous nickel particle surface prepared by presoma Face photo, show three-dimensional communication nano-porous structure.
Fig. 4 is the polarization curve of the hydrogen-precipitating electrode made of the three-dimensional communication nanoporous nickel being prepared in embodiment 1, is shown It has an excellent catalytic activity for hydrogen evolution.
Fig. 5 is with Mg70Pt20Ce10Non-crystaline amorphous metal is sweeping for three-dimensional communication nanoporous platinum grain surface prepared by presoma Retouch photo.
Fig. 6 is with Mg55Ni23Pt2Er20Non-crystaline amorphous metal is three-dimensional communication nanoporous nickel platinum grain table prepared by presoma The scanned photograph in face.
Fig. 7 is with Mg65Ag15La8Ce8Non-crystaline amorphous metal is three-dimensional communication nano-porous silver particle surface prepared by presoma Scanned photograph.
Embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.
A kind of three-dimensional communication nano porous metal of the present invention is with MgxMyNzNon-crystaline amorphous metal is presoma, by ammonium salt Removal alloying is carried out in solution and erodes Mg and N element to prepare.Wherein, one kind in M Cu, Ni, Pd, Pt, Au and Ag or More than one, N be lanthanide series similar in physicochemical properties (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Tb, Dy, Ho, Er, Tm, Yb and Lu) in one or more, x+y+z=100,40≤x≤90,5≤y≤40,5≤z≤40.In ammonium salt Anion is strong acid radical ion, such as (NH4)2SO4, NH4Cl, NH4NO3, NH4F, NH4Br, NH4Cl, NH4I, NH4MnO4Or NH4ClO4。
The three-dimensional communication nano porous metal for preparing the present invention comprises the steps of:
Step 1：Dispensing
According to MgxMyNzTarget component weighs Mg, M, N each element, and the mass percent purity of each element is not less than 99.0%；
Step 2：Melting prealloy
Load weighted M and N element in step 1 are well mixed, and melting is carried out in vacuum arc melting furnace, is obtained M-N prealloy ingots；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is≤5 × 10-2Pa；
Smelting temperature is 1000~3000 DEG C；
Smelting time：2~20min；
Step 3：Master alloy melting
Load weighted Mg in step 1 is mixed with obtaining M-N prealloy ingots in step 2, in high-frequency vacuum induction melting Melting in stove；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is≤5 × 10-2Pa；
Smelting temperature is 600~2000 DEG C；
Smelting time：5~15min；
Step 4：Prepare band
The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, it is melted completely It is ejected into afterwards at a high speed on the copper wheel of rotation, so as to which Mg be preparedxMyNzBand；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum is≤5 × 10-1Pa；
Smelting temperature is 500~1200 DEG C；
Smelting time：20~180s；
Injection pressure：0.01~0.1MPa；
Cooling velocity：10~105K/s。
Step 5：Removal alloying
Band obtained by step 4 is immersed in ammonium salt solution, removal alloying reaction occurs under ultrasonic state, so as to make Standby three-dimensional communication nano porous metal；
Etching condition：Temperature is 10~100 DEG C；
Ammonium salt concentration is the mol/L of 0.2 mol/L~2；
Ultrasonic power is 0~200 watt；
Etching time：5~120min.
The three-dimensional communication nano porous metal electrolysis water cathode hydrogen evolution electrode for preparing the present invention comprises the steps of：
Step A：Three-dimensional communication nano porous metal, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio Close, grinding, be ground to well mixed, obtain thick slurry, can add a certain amount of ethanol in mixed process plays dilution Effect, take a certain amount of slurry, and it is uniformly applied in nickel foam, obtain the nickel foam of carrying active material；
Step B：By the nickel foam of carrying active material in step A be placed in 40 DEG C of temperatures above baking ovens dry 5min with Taken out after the upper time, and be placed on tablet press machine under 1Mpa pressure above and carry out tabletting；
Step C：Nickel foam after being suppressed in step B is positioned in 40 DEG C of temperatures above baking ovens and continues to dry more than 1h, Then take out, obtain three-dimensional communication nano porous metal electrolysis water cathode hydrogen evolution electrode.
Embodiment 1
With Mg59Ni25La16Non-crystaline amorphous metal is that presoma prepares three-dimensional communication nanoporous nickel
Step 1：Dispensing
According to Mg59Ni25La16Target component weighs Mg, Ni, La each element, and the mass percent purity of each element is not less than 99.0%；
Step 2：Melting prealloy
Load weighted Ni and La elements in step 1 are well mixed, and melting is carried out in vacuum arc melting furnace, are obtained To Ni-La prealloy ingots；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 8 × 10-3Pa；
Smelting temperature is 1800 DEG C；
Smelting time：15min；
Step 3：Master alloy melting
Load weighted Mg in step 1 is mixed with obtaining Ni-La prealloy ingots in step 2, it is molten in high-frequency vacuum sensing Melting in furnace；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 1 × 10-2Pa；
Smelting temperature is 800 DEG C；
Smelting time：10min；
Step 4：Prepare band
The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, it is melted completely It is ejected into afterwards at a high speed on the copper wheel of rotation, so as to which Mg be prepared59Ni25La16Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum is 1 × 10-1Pa；
Smelting temperature is 700 DEG C；
Smelting time：30s；
Injection pressure：0.01MPa；
Cooling velocity：102K/s。
Step 5：Removal alloying
Band obtained by step 4 is immersed into (NH4)2SO4In solution, removal alloying reaction occurs under ultrasonic state, from And prepare three-dimensional communication nanoporous nickel；
Etching condition：Temperature is 50 DEG C；
Ammonium salt concentration is 1 mol/L；
Ultrasonic power is 100 watts；
Etching time is 30min.
By the presoma Mg of preparation59Ni25La16Product after band and its removal alloying is on D/MAX-2500 diffractometers Crystal species analysis is carried out, its result is as shown in Figure 1.Fig. 1 shows presoma Mg59Ni25La16Band has amorphous structure, goes to close The crystal peak of aurification product corresponds to face-centered cubic nickel.Removal alloying product is carried out in JSM7500 Flied emission surface sweeping Electronic Speculum Morphology observation, its result is as shown in Figures 2 and 3.Fig. 2 shows that product has floury structure, and particle diameter is in 15 microns.Figure 3 show that powder product has finer three-dimensional communication nano-porous structure.Fig. 1, Fig. 2 and Fig. 3 show to remove alloy in embodiment 1 Product after change is three-dimensional communication nanoporous nickel.On NOVA4200e types nitrogen adsorption-detachment assays instrument at a temperature of 77K The specific surface area for measuring removal alloying product is 63.8m2/g。
Using with Mg59Ni25La16Non-crystaline amorphous metal is that the three-dimensional communication nanoporous nickel that presoma obtains prepares electrolysis water the moon Pole hydrogen-precipitating electrode
Step A：Three-dimensional communication nanoporous nickel, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio, Grinding, grinding 10min obtain thick slurry to well mixed, added in mixed process 4 drop (8ml droppers) ethanol play it is dilute The effect released, 35g slurries are taken, and it is uniformly applied in nickel foam, obtain the nickel foam of carrying active material；
Step B：The nickel foam of carrying active material in step A is placed on after drying 30min in 120 DEG C of baking ovens and taken out, It is placed on tablet press machine under 10Mpa pressure and carries out tabletting；
Step C：Nickel foam after being suppressed in step B is positioned in 120 DEG C of baking ovens and continues to dry 24h, then takes out, obtains To three-dimensional communication nanoporous nickel electrowinning water cathode hydrogen evolution electrode.
The three-dimensional communication nanoporous nickel electrowinning water cathode hydrogen evolution electrode prepared in embodiment 1 is subjected to electro-chemical test, Comprise the following steps：
Electrochemistry experiment is on the electrochemical workstations of Princeton Applied Research VersaSTAT 3 in 25 Carried out at DEG C, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode is as reference Electrode, obtained three-dimensional communication nanoporous nickel electrowinning water cathode hydrogen evolution electrode is working electrode in embodiment 1, electrolyte 1 The KOH solution of mol/L.Potential value is scaled the potential value relative to reversible hydrogen electrode.The surface sweeping speed of electrochemical tests Rate is 0.1mV s-1.The electrochemical tests of acquisition are as shown in Figure 4.Fig. 4 shows, is reaching 100mA cm-2Current density In the case of, overpotential only has 46mV.Tafel slope as little as 21mV dec-1.Low overpotential and Tafel slope explanation are implemented The three-dimensional communication nanoporous nickel electrowinning water cathode hydrogen evolution electrode prepared in example 1 has excellent catalytic activity for hydrogen evolution.
Embodiment 2
With Mg70Pt20Ce10Non-crystaline amorphous metal is that presoma prepares three-dimensional communication nanoporous platinum
Step 1：Dispensing
According to Mg70Pt20Ce10Target component weighs Mg, Pt, Ce each element, and the mass percent purity of each element is not less than 99.0%；
Step 2：Melting prealloy
Load weighted Pt and Ce elements in step 1 are well mixed, and melting is carried out in vacuum arc melting furnace, are obtained To Pt-Ce prealloy ingots；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 1 × 10-2Pa；
Smelting temperature is 1600 DEG C；
Smelting time：10min；
Step 3：Master alloy melting
Load weighted Mg in step 1 is mixed with obtaining Pt-Ce prealloy ingots in step 2, it is molten in high-frequency vacuum sensing Melting in furnace；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 9 × 10-3Pa；
Smelting temperature is 900 DEG C；
Smelting time：15min；
Step 4：Prepare band
The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, it is melted completely It is ejected into afterwards at a high speed on the copper wheel of rotation, so as to which Mg be prepared70Pt20Ce10Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum is 8 × 10-2Pa；
Smelting temperature is 800 DEG C；
Smelting time：20s；
Injection pressure：0.05MPa；
Cooling velocity：103K/s。
Step 5：Removal alloying
Band obtained by step 4 is immersed into NH4In Cl solution, removal alloying reaction occurs under ultrasonic state, so as to make Standby three-dimensional communication nanoporous platinum；
Etching condition：Temperature is 20 DEG C；
Ammonium salt concentration is 1.5 mol/Ls；
Ultrasonic power is 50 watts；
Etching time is 40min.
By the presoma Mg of preparation70Pt20Ce10Product after band and its removal alloying is on D/MAX-2500 diffractometers Crystal species analysis is carried out, shows presoma Mg70Pt20Ce10Band has amorphous structure, and removal alloying product is Pt. Morphology observation is carried out to the removal alloying product in embodiment 2 in JSM7500 Flied emission surface sweeping Electronic Speculum, its result such as Fig. 5 institutes Show.Fig. 5 shows that the removal alloying product in embodiment 2 has finer three-dimensional communication nano-porous structure.
Using with Mg70Pt20Ce10Non-crystaline amorphous metal is that the three-dimensional communication nanoporous platinum that presoma obtains prepares electrolysis water the moon Pole hydrogen-precipitating electrode
Step A：Three-dimensional communication nanoporous platinum, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio, Grinding, grinding 20min obtain thick slurry to well mixed, added in mixed process 6 drop (8ml droppers) ethanol play it is dilute The effect released, 30g slurries are taken, and it is uniformly applied in nickel foam, obtain the nickel foam of carrying active material；
Step B：The nickel foam of carrying active material in step A is placed on after drying 40min in 100 DEG C of baking ovens and taken out, It is placed on tablet press machine under 5Mpa pressure and carries out tabletting；
Step C：Nickel foam after being suppressed in step B is positioned in 100 DEG C of baking ovens and continues to dry 48h, then takes out, obtains To three-dimensional communication nanoporous platinum electrolysis water cathode hydrogen evolution electrode.
The electro-chemical test of the three-dimensional communication nanoporous platinum electrolysis water cathode hydrogen evolution electrode prepared in embodiment 2 is included Following steps：
Electrochemistry experiment is on the electrochemical workstations of Princeton Applied Research VersaSTAT 3 in 25 Carried out at DEG C, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode is as reference Electrode, obtained three-dimensional communication nanoporous platinum electrolysis water cathode hydrogen evolution electrode is working electrode in embodiment 2, electrolyte 1 Mol/L KOH solution.Potential value converts in order to relative to the potential value of reversible hydrogen electrode.The surface sweeping speed of electrochemical tests Rate is 0.1mV s-1.As a result show, reaching 100mA cm-2In the case of current density, overpotential only has 20mV.Ta Feier Slope as little as 18mV dec-1.Low overpotential and Tafel slope illustrates the three-dimensional communication nanoporous platinum prepared in embodiment 2 Electrolysis water cathode hydrogen evolution electrode has excellent catalytic activity for hydrogen evolution.
Embodiment 3
With Mg55Ni23Pt2Er20Non-crystaline amorphous metal is that presoma prepares three-dimensional communication nanoporous nickel platinum
Step 1：Dispensing
According to Mg55Ni23Pt2Er20Target component weighs Mg, Ni, Pt, Er each element, the mass percent purity of each element Not less than 99.0%；
Step 2：Melting prealloy
Load weighted Ni, Pt and Er element in step 1 is well mixed, and melting is carried out in vacuum arc melting furnace, Obtain Ni-Pt-Er prealloy ingots；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 5 × 10-2Pa；
Smelting temperature is 1500 DEG C；
Smelting time：5min；
Step 3：Master alloy melting
Load weighted Mg in step 1 is mixed with obtaining Ni-Pt-Er prealloy ingots in step 2, sensed in high-frequency vacuum Melting in smelting furnace；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 7 × 10-3Pa；
Smelting temperature is 1000 DEG C；
Smelting time：5min；
Step 4：Prepare band
The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, it is melted completely It is ejected into afterwards at a high speed on the copper wheel of rotation, so as to which Mg be prepared55Ni23Pt2Er20Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum is 6 × 10-2Pa；
Smelting temperature is 1000 DEG C；
Smelting time：35s；
Injection pressure：0.1MPa；
Cooling velocity：104K/s。
Step 5：Removal alloying
Band obtained by step 4 is immersed into NH4NO3In solution, removal alloying reaction occurs under without ultrasonic state, so as to Prepare three-dimensional communication nanoporous nickel platinum；
Etching condition：Temperature is 100 DEG C；
Ammonium salt concentration is 3 mol/Ls；
Ultrasonic power is 0 watt；
Etching time is 25min.
By the presoma Mg of preparation55Ni23Pt2Er20Product after band and its removal alloying is in D/MAX-2500 diffractometers Upper carry out crystal species analysis, shows presoma Mg55Ni23Pt2Er20Band has amorphous structure, and removal alloying product is NiPt.Morphology observation is carried out to the removal alloying product in embodiment 3 in JSM7500 Flied emission surface sweeping Electronic Speculum, its result As shown in Figure 6.Fig. 6 shows that the removal alloying product in embodiment 3 has finer three-dimensional communication nano-porous structure.
Using with Mg55Ni23Pt2Er20Non-crystaline amorphous metal is that the three-dimensional communication nanoporous nickel platinum that presoma obtains prepares electrolysis Water cathode hydrogen evolution electrode
Step A：Three-dimensional communication nanoporous nickel platinum, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio Close, grinding, grinding 30min obtains thick slurry to being well mixed, and 8 drop (8ml droppers) ethanol are added in mixed process and are played The effect of dilution, 30g slurries are taken, and it is uniformly applied in nickel foam, obtain the nickel foam of carrying active material；
Step B：The nickel foam of carrying active material in step A is placed on after drying 20min in 50 DEG C of baking ovens and taken out, put Put and carry out tabletting under 2Mpa pressure on tablet press machine；
Step C：Nickel foam after being suppressed in step B is positioned in 50 DEG C of baking ovens and continues to dry 50h, then takes out, obtains To three-dimensional communication nanoporous nickel platinum electrolysis water cathode hydrogen evolution electrode.
By the electro-chemical test bag of the three-dimensional communication nanoporous nickel platinum electrolysis water cathode hydrogen evolution electrode prepared in embodiment 3 Containing following steps：
Electrochemistry experiment is on the electrochemical workstations of Princeton Applied Research VersaSTAT 3 in 25 Carried out at DEG C, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode is as reference Electrode, obtained three-dimensional communication nanoporous nickel platinum electrolysis water cathode hydrogen evolution electrode is working electrode in embodiment 3, and electrolyte is 1 mol/L KOH solution.Potential value converts in order to relative to the potential value of reversible hydrogen electrode.The surface sweeping speed of electrochemical tests Rate is 0.1mV s-1.As a result show, reaching 100mA cm-2In the case of current density, overpotential only has 35mV.Ta Feier Slope as little as 29mV dec-1.Low overpotential and Tafel slope illustrates the three-dimensional communication nanoporous nickel prepared in embodiment 3 Platinum electrolysis water cathode hydrogen evolution electrode has excellent catalytic activity for hydrogen evolution.
Embodiment 4
With Mg65Ag15La8Ce8Non-crystaline amorphous metal is that presoma prepares three-dimensional communication nano-porous silver
Step 1：Dispensing
According to Mg65Ag15La8Ce8Target component weighs Mg, Ag, La, Ce each element, the mass percent purity of each element Not less than 99.0%；
Step 2：Melting prealloy
Load weighted Ag, La and Ce element in step 1 is well mixed, and melting is carried out in vacuum arc melting furnace, Obtain Ag-La-Ce prealloy ingots；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 5 × 10-3Pa；
Smelting temperature is 2000 DEG C；
Smelting time：20min；
Step 3：Master alloy melting
Load weighted Mg in step 1 is mixed with obtaining Ag-La-Ce prealloy ingots in step 2, sensed in high-frequency vacuum Melting in smelting furnace；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum is 2 × 10-2Pa；
Smelting temperature is 1100 DEG C；
Smelting time：7min；
Step 4：Prepare band
The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, it is melted completely It is ejected into afterwards at a high speed on the copper wheel of rotation, so as to which Mg be prepared65Ag15La8Ce8Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum is 3 × 10-1Pa；
Smelting temperature is 750 DEG C；
Smelting time：40s；
Injection pressure：0.03MPa；
Cooling velocity：105K/s。
Step 5：Removal alloying
Band obtained by step 4 is immersed into NH4In Br solution, removal alloying reaction occurs under ultrasonic state, so as to make Standby three-dimensional communication nano-porous silver；
Etching condition：Temperature is 60 DEG C；
Ammonium salt concentration is 4 mol/Ls；
Ultrasonic power is 80 watts；
Etching time is 60min.
By the presoma Mg of preparation65Ag15La8Ce8Product after band and its removal alloying is in D/MAX-2500 diffractometers Upper carry out crystal species analysis, shows presoma Mg65Ag15La8Ce8Band has amorphous structure, and removal alloying product is Ag. Morphology observation is carried out to the removal alloying product in embodiment 4 in JSM7500 Flied emission surface sweeping Electronic Speculum, its result such as Fig. 7 institutes Show.Fig. 7 shows that the removal alloying product in embodiment 4 has finer three-dimensional communication nano-porous structure.
Using with Mg65Ag15La8Ce8Non-crystaline amorphous metal prepares electrolysis for the obtained three-dimensional communication nano-porous silver of presoma Water cathode hydrogen evolution electrode
Step A：Three-dimensional communication nano-porous silver, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio, Grinding, grinding 25min obtain thick slurry to well mixed, added in mixed process 5 drop (8ml droppers) ethanol play it is dilute The effect released, 25g slurries are taken, and it is uniformly applied in nickel foam, the nickel foam of carrying active material is obtained in air；
Step B：The nickel foam of carrying active material in step A is placed on after drying 25min in 70 DEG C of baking ovens and taken out, put Put and carry out tabletting under 6Mpa pressure on tablet press machine；
Step C：Nickel foam after being suppressed in step B is positioned in 70 DEG C of baking ovens and continues to dry 40h, then takes out, obtains To three-dimensional communication nano-porous silver electrolysis water cathode hydrogen evolution electrode.
The electro-chemical test of the three-dimensional communication nano-porous silver electrolysis water cathode hydrogen evolution electrode prepared in embodiment 4 is included Following steps：
Electrochemistry experiment is on the electrochemical workstations of Princeton Applied Research VersaSTAT 3 in 25 Carried out at DEG C, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode is as reference Electrode, obtained three-dimensional communication nano-porous silver electrolysis water cathode hydrogen evolution electrode is working electrode in embodiment 4, electrolyte 1 Mol/L KOH solution.Potential value converts in order to relative to the potential value of reversible hydrogen electrode.The surface sweeping speed of electrochemical tests Rate is 0.1mV s-1.As a result show, reaching 100mA cm-2In the case of current density, overpotential only has 69mV.Ta Feier Slope as little as 72mV dec-1.Low overpotential and Tafel slope illustrates the three-dimensional communication nano-porous silver prepared in embodiment 4 Electrolysis water cathode hydrogen evolution electrode has excellent catalytic activity for hydrogen evolution.
It should be noted that according to the various embodiments described above of the present invention, those skilled in the art are can to realize this hair completely The four corner of bright independent claims and appurtenance, implementation process and the same the various embodiments described above of method；And the present invention is not Elaborate and partly belong to techniques well known.
It is described above, part embodiment only of the present invention, but protection scope of the present invention is not limited thereto, and is appointed What those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in should all be covered Within protection scope of the present invention.

Claims (10)

  1. A kind of 1. three-dimensional communication nano porous metal, it is characterised in that：Three-dimensional communication nano porous metal is with MgxMyNzAmorphous closes Gold is presoma, erodes Mg and N element by carrying out removal alloying in ammonium salt solution, obtains three-dimensional communication nano-porous gold Category；
    The M is the one or more in Cu, Ni, Pd, Pt, Au and Ag；
    The N is the one or more in lanthanide series similar in physicochemical properties；The lanthanide series refer to La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Tb, Dy, Ho, Er, Tm, Yb and Lu；
    The MgxMyNzAtomic percentage x+y+z=100 in non-crystaline amorphous metal, 40≤x≤90,5≤y≤40,5≤z≤40.
  2. 2. three-dimensional communication nano porous metal according to claim 1, it is characterised in that：Described MgxMyNzNon-crystaline amorphous metal Presoma has the defects of amorphous structure, no crystal boundary, dislocation.
  3. 3. three-dimensional communication nano porous metal according to claim 1, it is characterised in that：Anion is in described ammonium salt Strong acid radical ion, the strong acid radical ion refer to (NH4)2SO4, NH4Cl, NH4NO3, NH4F, NH4Br, NH4Cl, NH4I, NH4MnO4 And NH4ClO4。
  4. 4. three-dimensional communication nano porous metal according to claim 1, it is characterised in that：Removal alloying process can be in ultrasound Carried out under state, power bracket is 0~200 watt, represents to carry out in the state of no ultrasound when power is 0.
  5. 5. three-dimensional communication nano porous metal according to claim 1, it is characterised in that：Hole knot with three-dimensional communication Structure, and specific surface area is to 63.8m2/g。
  6. A kind of 6. method for preparing three-dimensional communication nano porous metal, it is characterised in that comprise the steps of:
    Step 1：Dispensing
    According to MgxMyNzTarget component weighs Mg, M, N each element, and the mass percent purity of each element is not less than 99.0%；
    The MgxMyNzAtomic percentage x+y+z=100 in non-crystaline amorphous metal, 40≤x≤90,5≤y≤40,5≤z≤40；
    The M is the one or more in Cu, Ni, Pd, Pt, Au and Ag；
    The N be lanthanide series similar in physicochemical properties (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Tb, Dy, Ho, Er, Tm, Yb and Lu) in one or more；
    Step 2：Melting prealloy
    Load weighted M and N element in step 1 are well mixed, and melting is carried out in vacuum arc melting furnace, it is pre- to obtain M-N Alloy pig；
    Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
    Vacuum is≤5 × 10-2Pa；
    Smelting temperature is 1000~3000 DEG C；
    Smelting time：2~20min；
    Step 3：Master alloy melting
    Load weighted Mg in step 1 is mixed with obtaining M-N prealloy ingots in step 2, in high-frequency vacuum induction melting furnace Melting；
    Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
    Vacuum is≤5 × 10-2Pa；
    Smelting temperature is 600~2000 DEG C；
    Smelting time：5~15min；
    Step 4：Prepare band
    The foundry alloy obtained in step 3 is put into the vacuum induction melting furnace of quick solidification apparatus, sprayed after it is melted completely It is mapped at a high speed on the copper wheel of rotation, so as to which Mg be preparedxMyNzBand；
    Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
    Vacuum is≤5 × 10-1Pa；
    Smelting temperature is 500~1200 DEG C；
    Smelting time：20~180s；
    Injection pressure：0.01~0.1MPa；
    Cooling velocity：10~105K/s。
    Step 5：Removal alloying
    Band obtained by step 4 is immersed in ammonium salt solution, removal alloying reaction occurs under ultrasonic state, is received so as to prepare Rice porous metals；
    Etching condition：Temperature is 10~100 DEG C；
    Ammonium salt concentration is the mol/L of 0.2 mol/L~5；
    Ultrasonic power is 0~200 watt；
    Etching time：5~120min.
  7. 7. the method according to claim 5 for preparing three-dimensional communication nano porous metal, it is characterised in that：Described ammonium salt Middle anion is strong acid radical ion, such as (NH4)2SO4, NH4Cl, NH4NO3, NH4F, NH4Br, NH4Cl, NH4I, NH4MnO4, NH4ClO4。
  8. 8. a kind of method that three-dimensional communication nano porous metal using claim 1 prepares electrolysis water cathode hydrogen evolution electrode, its It is characterised by comprising the steps of：
    Step A：Three-dimensional communication nano porous metal, polytetrafluoroethylene (PTFE) and acetylene black are mixed according to certain ratio, ground Mill, is ground to well mixed, obtains thick slurry, the work that a certain amount of ethanol plays dilution can be added in mixed process With, a certain amount of slurry is taken, and it is uniformly applied in nickel foam, obtain the nickel foam of carrying active material；
    Step B：When the nickel foam of carrying active material in step A is placed in 40 DEG C of temperatures above baking ovens into dry more than 5min Between after take out, be placed on tablet press machine under 1Mpa pressure above and carry out tabletting；
    Step C：Nickel foam after being suppressed in step B is positioned in 40 DEG C of temperatures above baking ovens and continues to dry more than 1h, then Take out, obtain three-dimensional communication nano porous metal electrolysis water cathode hydrogen evolution electrode.
  9. 9. the method according to claim 7 for preparing electrolysis water cathode hydrogen evolution electrode, the three-dimensional communication nanometer being prepared Porous metals electrolysis water cathode hydrogen evolution electrode is reaching 100mA cm-2In the case of current density, overpotential only has 15~ 110mV, Tafel slope as little as 18~60mV dec-1。
  10. 10. three-dimensional communication nano porous metal according to claim 1, it is characterised in that：Hole knot with three-dimensional communication Structure, and specific surface area is to 63.8m2/g。
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CN108786853A (en) * 2018-06-13 2018-11-13 天津大学 Nano-porous catalyst method, nanoporous PdCuNi-S catalyst and purposes are prepared using crystal alloy
CN109023412A (en) * 2018-08-24 2018-12-18 北京科技大学 A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof
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CN108338161A (en) * 2018-01-30 2018-07-31 河北工业大学 A kind of supported porous silver oxide nanometer rod composite material of nano-porous silver and preparation method thereof
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CN108786853A (en) * 2018-06-13 2018-11-13 天津大学 Nano-porous catalyst method, nanoporous PdCuNi-S catalyst and purposes are prepared using crystal alloy
CN109055973A (en) * 2018-07-09 2018-12-21 太原理工大学 Aluminium adulterates three-D nano-porous metal sulfide hydrogen-precipitating electrode method of preparation and use
CN109023412A (en) * 2018-08-24 2018-12-18 北京科技大学 A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof
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