CN111254309B - Preparation method of nano porous metal or alloy - Google Patents
Preparation method of nano porous metal or alloy Download PDFInfo
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- CN111254309B CN111254309B CN202010142449.7A CN202010142449A CN111254309B CN 111254309 B CN111254309 B CN 111254309B CN 202010142449 A CN202010142449 A CN 202010142449A CN 111254309 B CN111254309 B CN 111254309B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23F1/00—Etching metallic material by chemical means
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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Abstract
The invention relates to a preparation method of nano porous metal or alloy, belonging to the technical field of nano metal, namely, selecting proper low-melting point metal and base metal, preparing precursor alloy through vacuum gas-phase alloying, controlling the thickness of an alloy layer and a generated alloy phase through controlling alloying time and temperature, and preparing a nano porous layer with corresponding thickness and structure in the subsequent dealloying process.
Description
Technical Field
The invention relates to a preparation method of nano-porous metal or alloy, belonging to the technical field of nano-metal.
Background
Since the 21 st century, the world energy system is in the process of rapid transformation and upgrading, and countries in the world are actively developing new energy by using new ideas and new modes. In the process of developing new energy, exploring, utilizing and developing various new materials and new technologies are just the high places in the scientific and technological field. In recent years, a novel metal nano material, namely, a nano porous metal prepared by using a dealloying method has a wide application potential in various scientific and technological fields, particularly catalysis, electrocatalysis, driving, energy conversion and storage and the like, which are rapidly developed at present, because of unique physical, chemical and mechanical properties, such as high specific surface area, good conductivity, high catalytic activity and the like.
With the development of science and technology, electronic equipment such as mobile phones, flat panels and electric vehicles is more and more popular, and the search for high-specific-capacity batteries is increasingly urgent. However, the specific capacity of the graphite negative electrode adopted by the lithium ion battery at present is only 372mAh g-1And far from meeting the increasing demand of people, the key to solving the problem is to improve the capacity of the cathode and find a new replaceable cathode. Lithium metal itself has up to 3860mAh g-1If the specific capacity of the lithium ion battery can be directly used as a battery cathode, the battery capacity is improved by ten times. However, one of the reasons that the application of the copper film is hindered is the generation of lithium dendrite in the circulation process, and the self-supporting three-dimensional nano-porous copper film prepared by gas-phase alloying and dealloying can be used as a current collector in a lithium metal battery to uniform the current density,thereby suppressing lithium dendrite formation.
In addition, since people burn fossil fuels such as petroleum, coal, etc., or fell down forests and burn them to generate a large amount of carbon dioxide, i.e., greenhouse gas, which is highly permeable to visible light from solar radiation and highly absorbent to long-wave radiation emitted from the earth, infrared rays in ground radiation are strongly absorbed, resulting in an increase in the temperature of the earth, i.e., greenhouse effect. Global warming can cause redistribution of global precipitation, ablation of glaciers and frozen earth, rise of sea level and the like, which not only endangers the balance of the natural ecosystem, but also threatens the survival of human beings. However, measures such as vehicle restriction and production suspension have short-term and local effects, and cannot fundamentally change climate warming and haze pollution. Therefore, reduction of carbon dioxide to a useful fuel gas using a catalyst is one of the approaches to solving this problem. The nano porous silver prepared by the method can be used as a high-efficiency catalyst for carbon dioxide reduction reaction.
The alloy is a material with metal characteristics formed by alloying two or more metal elements or metal-based addition of other non-metal elements. The existing metal alloying process mainly comprises smelting-solidification, mechanical alloying, sintering, vapor deposition and the like. Dealloying means that under a certain condition, metals with larger activity are dissolved due to the difference of electrochemical activity among different components in an alloy material, and relatively stable metals are subjected to diffusion recombination to obtain a porous structure. The dealloying includes chemical dealloying, electrochemical dealloying, liquid metal dealloying, gas phase dealloying, etc.
Compared with the prior related method for preparing the nano porous metal, the method for preparing the porous metal precursor is more traditional at present, mainly comprises vacuum melting and vacuum melt spinning or vacuum melting and pressure processing, and the precursor alloy prepared by the method has a single shape and cannot control the size. In addition, in general conditions, the alloy prepared by the method does not use pure metal as a substrate, and the nano-porous metal obtained after dealloying has poor mechanical properties and does not have self-supporting performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel metal alloying and nano-porous metal/alloy preparation method, develops a novel idea, has simple process and controllable components, can obtain nano-porous metal and alloy materials with different macro-scale and microstructure, and can realize large-scale production.
The technical scheme of the invention is as follows:
a preparation method of nano-porous metal or alloy comprises the following steps,
(1) the low-melting-point metal A and the substance B are selected, the substance B is transition metal or alloy, the substance B is used as base metal, and the substance B and the metal A can be alloyed through high-temperature annealing.
(2) Ultrasonically cleaning the substance B with acetone, ultrasonically cleaning with alcohol, and oven drying.
(3) A certain amount of metal A is placed in a quartz tube which can be subjected to vacuum tube sealing subsequently, and then a cleaned substance B is placed in the quartz tube, so that the metal A and the substance B are prevented from being in direct contact.
(4) Before the tube is sealed, the quartz tube is cleaned in a vacuumizing-argon filling mode, oxygen in the tube is completely discharged, and then the tube is sealed under the vacuum condition.
(5) According to the melting point of the metal A, annealing is carried out in a muffle furnace at a temperature which is higher than the melting point of the metal A but lower than the melting point of the substance B within the range of 400-1200 ℃, and the low-melting-point metal A and the substance B are subjected to a gas-phase alloying reaction to form an alloy of the metal A and the substance B;
if the alloying time is short or the temperature is low, a solid solution based on the substance B containing a small amount of the metal a may be formed, and if the time is long or the temperature is high, an intermetallic compound containing the metal a and the substance B may be formed.
(6) Performing dealloying treatment, wherein the treatment method is one of the following two methods:
processing one: if the electrochemical activity of the metal A is more active compared with that of the substance B, the alloy obtained in the step (5) can be put into an acidic or alkaline solution for chemical dealloying or electrochemical dealloying, the metal A in the alloy layer is selectively corroded, and atoms of the inert substance B form a nano-porous structure through a diffusion/self-assembly process; then further washing with deionized water to remove the electrolyte solution on the surface, then washing the substance B with absolute ethyl alcohol, and then drying in a vacuum drying oven to obtain a substance B with a nano-porous structure;
and (5) processing: and (4) putting the alloy obtained in the step (5) into a tube furnace, and performing vacuum dealloying by utilizing different metal evaporation points to finally obtain a substance B with a nano-porous structure. That is, the metal a is evaporated from the alloy layer by utilizing the difference in melting point without using the above chemical/electrochemical dealloying method, thereby forming the substance B having a nanoporous shape.
Preferably, in the step (1), the metal A is one of Mg, Zn, Bi and Cd, and the substance B is one of Ti, V, Cr, Co, Ni, Cu, Zr, Nb, Ru, Os, Ir, Rh, Mo, Pd, Ag, Hf, Ta, W, Pt and Au, or an alloy combination of two or more metals.
Preferably, in step (1), the metal A is in the form of powder, block, wire or foil, and the substance B is in the form of block, wire or foil.
Preferably, in step (1), the melting point of substance B is higher than the melting point of metal a. It is ensured that B ensures the integrity of the shape and reacts with the gas-turned metal a during the annealing process.
Preferably, in the step (2), the substance B is ultrasonically cleaned with acetone at room temperature in order to remove oil stains from the surface. And then cleaning the substance B with alcohol to remove residual acetone on the substance B, and drying the substance B.
Preferably, in the step (2), ultrasonic cleaning is performed for 10 minutes by using acetone, and then ultrasonic cleaning is performed for 10 minutes by using alcohol.
Preferably, in the step (3), in order to ensure that the material A and the material B can fully react after being changed into steam in the annealing process, the metal A in powder or block form is placed at the bottom of the quartz tube, and then the material B in foil, wire or block form is fixedly placed in the middle of the quartz tube by using a specific quartz device, and the quartz tube is vertically placed to avoid direct contact between the metal A and the material B.
Preferably, in the step (4), after the quartz tube with the sample placed therein is connected to the vacuum tube sealing machine, in order to avoid the influence of oxygen on the sample and the gas-phase alloying process, the quartz tube is subjected to vacuum-argon filling operation for 5 times continuously to minimize the influence of oxygen, and then the tube sealing operation is performed under a vacuum condition.
Preferably, in the step (5), the temperature of the gas-phase alloying is 400-1200 ℃, the time is 1-30 h, and the alloying is performed under the vacuum condition.
Preferably, in the step (6), the alkaline solution is one of NaOH and KOH, and the acidic solution is H2SO4、HCl、HNO3One kind of (1).
Preferably, in the step (6), the concentration of the alkaline solution or the acidic solution used for the electrochemical dealloying and the chemical dealloying is 0.1-5 mol/L, the temperature is 20-90 ℃, and the corrosion time is 0.5-20 h. The size of the porous ligament is influenced by the potential, the concentration and the type of the electrolyte selected for the electrochemical corrosion. The type of solution selected for chemical etching and the concentration also have an effect on the porous morphology. Different parameters are selected according to different metals.
Preferably, in the step (6), vacuum dealloying is performed in a tube furnace with the vacuum degree of less than 50Pa, the dealloying temperature is 450-800 ℃, and the time is 0.5-3 h. Forming a nano-porous structure on the bulk, filamentous or film metal B, wherein the size of the nano-pores is 3-500 nm.
The invention has the beneficial effects that:
the invention reasonably utilizes the characteristic that low-melting point metal is easy to react with other metals to form alloy at a certain temperature, prepares a specific alloy product by annealing by utilizing a binary alloy phase diagram, and obtains the metal or alloy with a nano porous structure by dealloying treatment, and has the following advantages that:
(1) the precursor alloy is prepared by vacuum gas-phase alloying, the thickness of the alloy layer is controlled by controlling the alloying time and temperature, so that the nano porous layer with corresponding thickness is prepared in the subsequent dealloying process, and because the metal or alloy with a certain shape can be used as a substrate, the original self-supporting performance of the material can be kept, the nano porous layer is simple and controllable, the large-scale production can be realized, and different alloy phases can be generated in the alloying process by further controlling the temperature and time, so that the ligament size of the porous structure can be controlled. (2) The precursor alloy obtained by vacuum gas-phase alloying has flexible shape, and can be a block, a thin film and a line, and the thin film can also be any area and shape. (3) The obtained precursor alloy can be subjected to dealloying by using the reaction of acid and alkali solutions with common concentrations or by utilizing the characteristic of low evaporation point because metals such as zinc, magnesium, cadmium, bismuth and the like are relatively active or have relatively low evaporation point. (4) The method can get rid of the limitation of the shape of the previous nano porous metal material, prepare the nano porous metal material in sheet shape, linear shape, block shape and various shapes, and obtain the nano porous filaments, films and blocks with different shapes by random collocation of single-phase transition metal or multi-phase alloy and zinc, magnesium, bismuth and cadmium and then dealloying. (5) The obtained nano porous metal material is a potential catalytic material, has wide application prospect in energy conversion and storage, and can be applied to the fields of catalysis, electrocatalysis, driving, energy conversion and storage and the like.
Drawings
FIG. 1 shows the surface macro-photographs of Ag-Zn alloy obtained by alloying pure Ag, Ag and Zn and nano-porous Ag after dealloying in the example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of Ag-Zn alloy obtained after alloying in example 1 of the present invention. Wherein the abscissa is angle and the ordinate is intensity.
FIG. 3 is an X-ray diffraction pattern of the nanostructured metal Ag obtained after the dealloying in example 1 of the present invention. Wherein the abscissa is angle and the ordinate is intensity.
FIG. 4 is a scanning electron micrograph of the nanostructured metal Ag obtained after the dealloying in example 1 of the present invention.
Detailed Description
The present invention will be further described by way of examples, but not limited thereto, with reference to the accompanying drawings.
Example 1:
a preparation method of the nano-porous silver foil comprises the following steps:
(1) cutting a silver foil with a certain size to be used as a substance B, and selecting zinc powder as metal A;
(2) and (3) putting the cut silver foil into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the silver foil, putting the silver foil into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, and taking out and drying the silver foil.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned silver foil on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, carrying out vacuumizing-argon filling operation on the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 500 ℃, setting the heating time to be 10 hours, reacting and alloying the zinc powder and the silver foil, and taking out the quartz tube when the muffle furnace is cooled to the room temperature.
(6) Alloying silver foil at 0.1mol/L H2SO4And carrying out electrochemical corrosion in the solution, wherein the calomel electrode and the graphite are respectively used as a reference electrode and a counter electrode, and the working electrode is prepared silver-zinc alloy foil. The corrosion temperature is room temperature, the corrosion potential is 0.15V (vs. SCE), the silver foil is taken out when the current is obviously reduced, the silver foil is respectively cleaned by deionized water and absolute ethyl alcohol and is placed in a vacuum drying oven for drying for 12 hours at the temperature of 60 ℃, the water and the alcohol in the porous silver foil are completely evaporated to dryness, and a corrosion product only containing pure silver is obtained, namely the silver with the nano structure is obtained, and the size of the ligament is 300-500 nm.
Fig. 3 is an XRD pattern of the resulting product, from which it can be seen that the resulting sample is a uniform silver foil.
FIG. 4 is a scanning electron microscope image of the obtained product, from which it can be seen that the obtained sample is a uniform nanoporous structure with ligament size of 300-500 nm.
In this example, the macroscopic photographs of the surface of pure Ag, Ag-Zn alloy obtained after alloying Ag and Zn, and nano-porous Ag after dealloying are shown in fig. 1, and it can be seen from fig. 1 that the original Ag surface is smooth and has metallic luster, and after dealloying, the surface becomes rough but still has a certain metallic luster, and after further dealloying, the color becomes pure white, and the metallic luster disappears, indicating that the Ag with nano-porous structure is obtained.
Example 2
A preparation method of a nano-porous cobalt foil comprises the following steps:
(1) cutting a cobalt foil with a certain size as a substance B, and selecting zinc powder as metal A;
(2) and (3) putting the cut cobalt foil into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the cobalt foil, putting the cobalt foil into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, taking out the cobalt foil, and drying the cobalt foil by using a blower.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned cobalt foil on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, vacuumizing and filling argon into the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 500 ℃, setting the heating time to be 30 hours, converting the zinc powder into zinc steam, reacting with the cobalt foil, alloying, and taking out the zinc steam and the cobalt foil when the temperature of the muffle furnace is cooled to room temperature.
(6) And (3) placing the alloyed cobalt foil in a tube furnace for vacuum dealloying at the temperature of 600 ℃, the vacuum degree of less than 50Pa and the time of 0.5h to obtain a product only containing pure cobalt, namely the cobalt with the nano porous structure, wherein the ligament size is 20-500 nm.
Example 3
A preparation method of a nano-porous gold foil comprises the following steps:
(1) cutting a gold foil with a certain size to be used as a substance B, and selecting zinc powder as metal A;
(2) and (3) putting the cut gold foil into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the gold foil, putting the gold foil into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, taking out the gold foil, and drying the gold foil by using a blower.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned gold foil on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, vacuumizing and filling argon into the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 500 ℃, setting the heating time to be 10 hours, converting the zinc powder into zinc vapor, reacting with the gold foil, alloying, and taking out the zinc vapor and the gold foil when the temperature of the muffle furnace is cooled to room temperature.
(6) And chemically corroding the alloyed gold foil in 5mol/L NaOH solution at the corrosion temperature of 30 ℃ for 10 hours, washing with deionized water and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours, and completely evaporating the water and alcohol in the porous gold foil to dryness to obtain a corrosion product only containing pure gold, namely the nano porous gold with the ligament size of 3-50 nm.
Example 4
A preparation method of a nano porous gold-silver alloy foil comprises the following steps:
(1) cutting a gold-silver alloy foil with a certain size to be used as a substance B, and selecting zinc powder as a metal A;
(2) and putting the cut alloy foil into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the gold-silver alloy foil, putting the gold-silver alloy foil into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, taking out the alloy foil, and drying the alloy foil by using a blower.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned alloy foil on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, vacuumizing and filling argon into the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 500 ℃, setting the heating time to be 20 hours, converting the zinc powder into zinc vapor, reacting with the alloy foil, alloying, and taking out the zinc vapor when the temperature of the muffle furnace is cooled to room temperature.
(6) And chemically corroding the alloyed metal foil in 2mol/L HCl solution at the corrosion temperature of 60 ℃ for 6 hours, cleaning with deionized water and alcohol, placing in a vacuum drying oven for drying at the temperature of 60 ℃ for 12 hours, and completely evaporating the water and alcohol in the porous alloy foil to dryness to obtain a corrosion product only containing gold and silver, namely the alloy foil with the nano structure, wherein the size of the ligament is 10-60 nm.
Example 5
A preparation method of a nano porous silver wire comprises the following steps:
(1) cutting a silver wire with a certain length to be used as a substance B, and selecting zinc powder as metal A;
(2) and putting the cut silver wires into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the silver wires, putting the silver wires into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, taking out the silver wires, and drying the silver wires by using a blower.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned silver wire on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, vacuumizing and filling argon into the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 800 ℃, setting the heating time to be 5 hours, converting the zinc powder into zinc vapor, reacting and alloying the zinc vapor with the silver wire, and taking out the quartz tube when the temperature of the muffle furnace is cooled to the room temperature.
(6) Alloying metal wire at 1mol/L HNO3And (3) carrying out chemical corrosion in the solution, wherein the corrosion temperature is 30 ℃, the corrosion time is 0.5h, taking out the silver wire after no bubbles exist, cleaning the silver wire by using deionized water and alcohol, placing the silver wire in a vacuum drying oven for drying for 12h at the temperature of 60 ℃, and completely evaporating the water in the silver wire to dryness to obtain the silver wire with the nano structure, wherein the ligament size is 10-500 nm.
Example 6
A preparation method of a nano porous silver block comprises the following steps:
(1) cutting a silver block with a certain shape to be used as a substance B, and selecting zinc powder as metal A;
(2) putting the silver blocks into a beaker filled with acetone, carrying out ultrasonic oscillation for 10 minutes, taking out the silver blocks, putting the silver blocks into a beaker filled with alcohol, carrying out ultrasonic oscillation for 10 minutes, taking out the silver blocks, and drying the silver blocks by using a blower.
(3) Weighing zinc powder with a certain mass, placing the zinc powder at the bottom of a quartz tube by using a long glass tube to prevent the zinc powder from being bonded on the tube wall of the quartz tube, then placing the quartz tube into a quartz bracket, and finally placing a cleaned silver block on the quartz bracket.
(4) Connecting the quartz tube to a vacuum tube sealing machine, vacuumizing and filling argon into the quartz tube, cleaning for 5 times, discharging residual air in the tube, and then sealing the tube in a vacuum state.
(5) And vertically placing the sealed quartz tube into a muffle furnace, setting the gas-phase alloying temperature to be 1200 ℃, setting the heating time to be 5 hours, converting the zinc powder into zinc vapor, reacting with the silver blocks, alloying, and taking out the quartz tube when the temperature of the muffle furnace is cooled to room temperature.
(6) And chemically corroding the alloyed alloy block in 2mol/L HNO3 solution at the corrosion temperature of 20 ℃ for 20 hours, taking out the silver block after no bubbles exist, cleaning the silver block with deionized water and alcohol, placing the silver block in a vacuum drying oven at the temperature of 60 ℃ for drying for 12 hours, and completely drying the water in the silver block to obtain the silver block with the nano porous structure, wherein the ligament size is 200-500 nm.
Example 7
Compared with the preparation method of the nano-porous copper foil in the embodiment 1, the preparation method is the same as the embodiment 1 except that magnesium particles are used as metal A and copper foil is used as a substance B as raw materials, the alloying temperature in the step (5) is 800 ℃, the heating time is 1h, the working electrode in the step (6) is copper-zinc alloy foil, the corrosion voltage is 0.1V (vs. SCE), the obtained corrosion product is copper with a nano-porous structure, and the size of a ligament is 20-500 nm.
Example 8
Compared with the embodiment 1, the preparation method of the nano-porous vanadium foil is the same as the embodiment 1 except that the vanadium foil is used as a raw material B, the alloying temperature in the step (5) is 500 ℃, the heating time is 20 hours, the working electrode in the step (6) is the prepared vanadium-zinc alloy foil, the corrosion voltage is 0.2V (vs. SCE), the obtained corrosion product is vanadium with a nano-porous structure, and the ligament size is 300-500 nm.
Example 9
Compared with the embodiment 2, the preparation method of the nano porous nickel foil is the same as the embodiment 2 except that cadmium particles are used as metal A and the nickel foil is used as a substance B as raw materials, the gas phase alloying temperature in the step (5) is 400 ℃ for 20 hours, the vacuum dealloying temperature in the step (6) is 450 ℃ for 3 hours, the obtained corrosion product is nickel with a nano porous structure, and the ligament size is 5-15 nm.
Example 10
Compared with the embodiment 2, the preparation method of the nano porous platinum foil is the same as the embodiment 2 except that bismuth particles are used as the metal A and the platinum foil is used as the substance B as raw materials, the gas phase alloying temperature in the step (5) is 1000 ℃ for 10 hours, the vacuum dealloying temperature in the step (6) is 800 ℃ for 2 hours, the obtained corrosion product is platinum with a nano porous structure, and the ligament size is 3-10 nm.
Example 11
Compared with the embodiment 3, the preparation method of the nano-porous zirconium foil is the same as the embodiment 3 except that the zirconium foil is used as a raw material B, the gas-phase alloying temperature in the step (5) is 500 ℃, the time is 20 hours, the corrosion solution in the step (6) is 0.5mol/L KOH solution, the corrosion time is 20 hours, the corrosion temperature is 50 ℃, the obtained corrosion product is zirconium with a nano-porous structure, and the ligament size is 50-200 nm.
Example 12
Compared with the preparation method of the nano porous chromium foil in the embodiment 3, except that magnesium particles are used as the metal A and the chromium foil is used as the substance B as the raw materials, the gas-phase alloying temperature in the step (5) is 800 ℃, the time is 10 hours, and the etching solution in the step (6) is 0.2mol/L of HNO3The solution is etched for 20 hours at 90 ℃, the obtained corrosion product is chromium with a nano-porous structure, the ligament size is 50-200 nm, and the rest is the same as that of the embodiment 3.
Example 13
Compared with the preparation method of the nano porous hafnium foil in the embodiment 3, except that the hafnium foil is used as the substance B as the raw material, the etching solution in the step (6) is 0.2mol/L HNO3The solution is etched for 10 hours, the obtained etched product is hafnium with a nano-porous structure, the ligament size is 50-200 nm, and the rest is the same as that of the embodiment 3.
Example 14
Compared with the preparation method of the nano-porous niobium foil in the embodiment 3, the preparation method of the nano-porous niobium foil adopts the niobium foil as the material B, and the etching solution in the step (6) is 2mol/L of H2SO4The solution, the corrosion product obtained is nano-structured niobium, the ligament size is 50-300 nm, and the rest is the same as the embodiment 3.
Example 15
Compared with the embodiment 3, the preparation method of the nano-porous tungsten foil is the same as the embodiment 3 except that the tungsten foil is used as the material B, the corrosion solution in the step (6) is 2mol/L KOH solution, the obtained corrosion product is tungsten with a nano structure, and the ligament size is 50-300 nm.
Example 16
Compared with the embodiment 3, the preparation method of the nano-porous ruthenium foil is the same as the embodiment 3 except that the ruthenium foil is used as a material B as a raw material, the corrosion product obtained in the step (6) is ruthenium with a nano-porous structure, and the ligament size is 50-200 nm.
Example 17
Compared with the preparation method of the nano-porous iridium foil in the embodiment 3, the preparation method is the same as the embodiment 3 except that the iridium foil is used as a material B as a raw material, the corrosion solution in the step (6) is 2mol/L HCl, the corrosion temperature is 50 ℃, the obtained corrosion product is nano-structured iridium, and the ligament size is 50-300 nm.
Example 18
Compared with the preparation method of the nano-porous rhodium foil in the embodiment 3, the preparation method is the same as the embodiment 3 except that the rhodium foil is used as a material B, the corrosion solution in the step (6) is 1mol/L HCl, the corrosion temperature is 50 ℃, the obtained corrosion product is nano-structured rhodium, and the ligament size is 20-200 nm.
Example 19
Compared with the embodiment 4, the preparation method of the nano-porous gold-copper alloy foil has the advantages that the gold-copper alloy foil is used as the substance B except for the raw material, and the etching solution in the step (6) is 0.5mol/L HNO3The corrosion temperature is 30 ℃, the obtained corrosion product is gold-copper alloy foil with a nano structure, the ligament size is 20-200 nm, and the rest is the same as that of the embodiment 4.
Example 20
Compared with the preparation method of the nano-porous copper wire in the embodiment 5, the preparation method of the nano-porous copper wire has the advantages that the copper wire is used as a substance B, and the corrosion solution in the step (6) is 0.5mol/L HNO3The corrosion product is copper wire with nano structure, except ligament size of 200-500 nm, the rest is the same as example 5.
Claims (10)
1. A preparation method of nano-porous metal or alloy is characterized by comprising the following steps:
(1) selecting a low-melting-point metal A and a substance B, wherein the substance B is a transition metal or an alloy, and the substance B is used as a base metal; the metal A is in a powdery shape, a block shape, a filiform shape or a foil shape, and the substance B is in a block shape, a filiform shape or a foil shape;
the metal A is one of Mg, Zn, Bi and Cd;
(2) ultrasonically cleaning a substance B with a specific shape by using acetone, ultrasonically cleaning by using alcohol, and then drying;
(3) firstly, a certain amount of metal A is placed in a quartz tube, and then a cleaned substance B is placed in the quartz tube, so that the metal A and the substance B are prevented from being in direct contact;
(4) before sealing the tube, cleaning the quartz tube in a vacuumizing-argon filling mode, completely discharging oxygen in the tube, and then sealing the tube under a vacuum condition;
(5) according to the melting point of the metal A, annealing is carried out in a muffle furnace at a temperature which is higher than the melting point of the metal A but lower than the melting point of the substance B within the range of 400-1200 ℃, and the low-melting-point metal A and the substance B are subjected to a gas-phase alloying reaction to form an alloy of the metal A and the substance B;
(6) performing dealloying treatment, wherein the treatment method is one of the following two methods:
processing one: if the electrochemical activity of the metal A is more active compared with that of the substance B, the alloy obtained in the step (5) is put into an acidic or alkaline solution for chemical dealloying or electrochemical dealloying, the metal A in the alloy layer is corroded, and atoms of the inert substance B form a nano-porous structure through a diffusion/self-assembly process; then further washing with deionized water to remove the electrolyte solution on the surface, then washing the substance B with absolute ethyl alcohol, and then drying in a vacuum drying oven to obtain a substance B with a nano-porous structure;
and (5) processing: and (4) putting the alloy obtained in the step (5) into a tube furnace, and performing vacuum dealloying by utilizing different metal evaporation points to finally obtain a substance B with a nano-porous structure.
2. The method according to claim 1, wherein in the step (1), the material B is one or an alloy of two or more metals selected from Ti, V, Cr, Co, Ni, Cu, Zr, Nb, Ru, Os, Ir, Rh, Mo, Pd, Ag, Hf, Ta, W, Pt and Au.
3. The method for preparing a nanoporous metal or alloy according to claim 1, wherein in step (2) the substance B is ultrasonically cleaned with acetone at room temperature.
4. The method for preparing a nanoporous metal or alloy according to claim 3, wherein in step (2), the metal or alloy is ultrasonically cleaned with acetone for 10 minutes and then with alcohol for 10 minutes.
5. The method for preparing a nanoporous metal or alloy according to claim 1, wherein in step (3), the metal A is disposed at the bottom of the quartz tube, and the material B is disposed at the middle of the quartz tube with a fixture, and the quartz tube is vertically disposed to avoid direct contact between the metal A and the material B.
6. The method for preparing a nanoporous metal or alloy according to claim 1, wherein in the step (4), after the sample-containing quartz tube is connected to a vacuum tube sealing machine, the quartz tube is subjected to vacuum-argon filling operation for 5 times, and then the tube sealing operation is performed under vacuum.
7. The method for preparing a nanoporous metal or alloy according to claim 1, wherein the step (5) is performed under vacuum at 400-1200 ℃ for 1-30 hours.
8. The method of claim 1, wherein in step (6), the alkaline solution is one of NaOH and KOH, and the acidic solution is H2SO4、HCl、HNO3One kind of (1).
9. The method for preparing nanoporous metal or alloy according to claim 8, wherein in the step (6), the concentration of the alkaline solution or acidic solution used for electrochemical dealloying and chemical dealloying is 0.1-5 mol/L, the temperature is 20-90 ℃, and the corrosion time is 0.5-20 h.
10. The method for preparing the nanoporous metal or alloy according to claim 1, wherein the vacuum dealloying is performed in a tube furnace with a vacuum degree of less than 50Pa in the step (6), and the dealloying temperature is 450 ℃ to 800 ℃ and the time is 0.5 to 3 hours.
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| CN112342478B (en) * | 2020-11-06 | 2022-02-08 | 西北有色金属研究院 | Preparation method of nano-porous titanium alloy film |
| CN113122871A (en) * | 2021-03-07 | 2021-07-16 | 南京大学 | Preparation method and application of bimetallic porous nano-material catalyst |
| CN113800899A (en) * | 2021-08-12 | 2021-12-17 | 西安理工大学 | Preparation method of bulk nano-porous CuO |
| CN114134362A (en) * | 2021-11-18 | 2022-03-04 | 昆明理工大学 | Preparation method of large-size high-strength three-stage composite porous magnesium-silver alloy |
| CN114400331A (en) * | 2022-03-03 | 2022-04-26 | 电子科技大学 | Preparation method of negative current collector capable of improving lithium metal cycle stability |
| CN115852194B (en) * | 2022-11-29 | 2024-05-03 | 上海交通大学 | Preparation method of multistage nano porous metal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325999A (en) * | 2013-05-22 | 2013-09-25 | 吉林大学 | Preparation method of seamlessly integrated metal substrate/nanoporous metal/metal oxide composite electrode material, and application of compound electrode material |
| CN108118227A (en) * | 2017-11-09 | 2018-06-05 | 广德宝达精密电路有限公司 | Nano-magnesium-based hydrogen storage material for high-energy solid battery and preparation method thereof |
| CN109373795A (en) * | 2018-11-14 | 2019-02-22 | 上海大学 | There is the method for the high heat transfer rate heat transfer pipe of porous structure liner using the preparation of high temperature elements vaporization technique |
-
2020
- 2020-03-04 CN CN202010142449.7A patent/CN111254309B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325999A (en) * | 2013-05-22 | 2013-09-25 | 吉林大学 | Preparation method of seamlessly integrated metal substrate/nanoporous metal/metal oxide composite electrode material, and application of compound electrode material |
| CN108118227A (en) * | 2017-11-09 | 2018-06-05 | 广德宝达精密电路有限公司 | Nano-magnesium-based hydrogen storage material for high-energy solid battery and preparation method thereof |
| CN109373795A (en) * | 2018-11-14 | 2019-02-22 | 上海大学 | There is the method for the high heat transfer rate heat transfer pipe of porous structure liner using the preparation of high temperature elements vaporization technique |
Non-Patent Citations (2)
| Title |
|---|
| 《纳米多孔合金的去合金化工艺研究》;李大鹏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215(第 S1 期);正文第1-15页 * |
| The design of ZnSyAgyZnS transparent conductive multilayer films;Xuanjie Liu等;《Thin Solid Films》;20031231;第441卷(第3期);200-206 * |
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