CN112957912B - Multilayer selective hydrogen permeation composite membrane and preparation and application thereof - Google Patents
Multilayer selective hydrogen permeation composite membrane and preparation and application thereof Download PDFInfo
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- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention provides a multilayer selective hydrogen permeation composite membrane, and belongs to the technical field of hydrogen permeation. The graphene film comprises a metal substrate layer with high hydrogen transmission rate, a metal layer with catalytic activity and permeability to hydrogen and a single-layer graphene film with selective permeability to proton hydrogen; the metal substrate layer is niobium or a metal alloy consisting of niobium and other metal elements, and the metal layer is palladium or a metal alloy consisting of palladium and other elements. The invention also provides a preparation method of the multilayer selective hydrogen permeation composite membrane. The multilayer selective hydrogen permeation composite membrane can effectively prevent the high-temperature mutual diffusion of metal atoms in the metal layer and metal atoms in the metal substrate layer, does not influence the hydrogen permeation rate of the composite membrane, and can prolong the service life of the composite membrane. The multilayer selective hydrogen permeation composite membrane material of the present invention is particularly useful for separating hydrogen from a gas mixture by selective diffusion.
Description
Technical Field
The invention relates to the technical field of hydrogen permeation, in particular to a multilayer selective hydrogen permeation composite membrane and preparation and application thereof.
Background
In the process of recycling deuterium-tritium fuel of a controlled thermonuclear fusion reactor and the process of hydrogen production, hydrogen storage and hydrogen-oxygen fuel cell by utilizing advanced hydrogen energy, the operation of effectively separating and further purifying hydrogen or isotopes (deuterium and tritium) thereof from the contained mixed gas is greatly involved. The membrane separation technology, as a relatively new and rapidly developed technology, has the advantages of energy conservation, environmental protection, low cost and the like, and is widely applied to the industry. The dense metal membrane is considered as an ideal hydrogen separation membrane material of the next generation because of its advantages such as high hydrogen selective separation, good mechanical strength, and easy molding. Palladium and its alloy membranes are commercially common hydrogen separation membranes, but their high price limits their widespread use. The VB group transition metals such as niobium and the like have the advantages of low cost, high hydrogen permeability coefficient, good mechanical strength and the like, but the surfaces of the transition metals lack the dissociation capability on hydrogen molecules. The palladium-niobium-palladium composite membrane formed by combining palladium and niobium is considered as an ideal hydrogen separation and purification material of the next generation due to good hydrogen permeability and mechanical properties. However, at high temperatures, the palladium and niobium atoms readily interdiffuse to form NbPd 3 Compounds, which in turn severely reduce the hydrogen permeability of the composite membrane. Therefore, it is desirable to design a composite membrane that can block the interdiffusion of palladium and niobium atoms at high temperature without affecting the hydrogen permeability.
In order to solve the problem of interdiffusion of palladium and niobium atoms at high temperature, the researchers have attempted to use metal surface layer carbonization, nitridation, etc. to prevent interdiffusion between palladium and group VB transition metals by using metal carbides or nitrides. The research shows that: niobium carbide, niobium nitride, hafnium nitride and the like can prevent the mutual diffusion of palladium and niobium, vanadium and tantalum atoms; however, the hydrogen permeability of the prepared composite membrane is greatly reduced. Therefore, it is difficult to obtain a composite membrane having high hydrogen permeability by a method of interposing a metal carbide or nitride into the interface between palladium and a group VB metal. The single-layer graphene film is a quasi-two-dimensional film material which is composed of carbon atoms, is infinitely and repeatedly arranged on a two-dimensional plane according to a regular hexagonal honeycomb crystal structure, has the thickness of only a single atomic layer, and has the heat resistance of more than 1400K. The interlayer can effectively prevent the mutual diffusion between palladium and other metal (such as ruthenium) atoms. Meanwhile, the graphene film has good hydrogen overflow effect and proton hydrogen selective permeability. When a transition metal catalyst (palladium, platinum, or the like) is supported on the surface of the graphene film and hydrogen molecules are dissociated, hydrogen protons dissociated migrate from the surface of the transition metal to the graphene film, diffuse and migrate along the carbon six-membered ring, and finally permeate through the graphene film.
Disclosure of Invention
The invention aims to solve the problem that hydrogen permeability is seriously reduced due to high-temperature mutual diffusion of palladium and niobium atoms, and provides a multilayer selective hydrogen permeation composite membrane and preparation and application thereof. The multilayer selective hydrogen permeation composite membrane can effectively prevent the high-temperature mutual diffusion of palladium and niobium atoms, does not influence the hydrogen permeation rate of the composite membrane, and prolongs the service life of the composite membrane.
The purpose of the invention is realized by the following technical scheme:
a multilayer selective hydrogen permeation composite membrane comprises a metal substrate layer with high hydrogen permeability, a metal layer with catalytic activity and permeability to hydrogen and a single-layer graphene membrane with selective permeability to proton hydrogen; the metal substrate layer is niobium or a metal alloy consisting of niobium and other metal elements, and the metal layer is palladium or a metal alloy consisting of palladium and other elements.
Further, the single-layer graphene film is grown on the copper substrate by a CVD method.
Further, the composite film comprises a metal layer, a single-layer graphene film, a metal substrate layer, a single-layer graphene film and a metal layer in sequence.
The application discloses a multilayer selective hydrogen permeation composite membrane of a metal layer/a single-layer graphene membrane/a metal substrate layer/a single-layer graphene layer/a metal layer, wherein the single-layer graphene membrane is used as an intermediate layer. The high-temperature thermal stability and the interface barrier property of the single-layer graphene film are utilized to prevent the metal atoms in the metal layer and the metal atoms in the metal substrate layer from mutually diffusing at high temperature, and meanwhile, the proton permeation specificity and the hydrogen overflow effect of the single-layer graphene film are utilized to ensure the hydrogen permeability of the composite film.
Further, the metal substrate layer is niobium or a metal alloy consisting of niobium and one or more of titanium, nickel, tantalum, zirconium, hafnium and cobalt metal elements.
Furthermore, the crystal form of the metal base material layer is any one of single crystal, nano crystal or micro crystal, and the grain size of the metal base material layer is 20 nm-200 mu m. The metal substrate layer is preferably a nanocrystalline metal substrate layer with the grain size of 20-100 nm.
Furthermore, the metal layer is a continuous or discontinuous metal alloy film consisting of palladium or palladium and nickel, ruthenium and copper elements, and the thickness of the metal layer is less than 200 nm.
A method for preparing a multilayer selective hydrogen permeation composite membrane, comprising the steps of:
1) surface treatment of metal substrate layer
Removing most of the oxide layer on the surface of the metal substrate layer, and then carrying out cold air blow-drying for later use after electrolytic polishing and ultrasonic cleaning;
2) transfer of single layer graphene films
Transferring the prefabricated single-layer graphene film to the surface of the metal base material layer after surface treatment by adopting a rapid transfer method to prepare a single-layer graphene film/metal base material layer composite film;
3) deposition of metal layers
Sputtering a layer of metal film on the single-layer graphene film surface of the single-layer graphene film/metal base material layer composite film by adopting a magnetron sputtering method to form a metal layer/single-layer graphene film/metal base material layer composite film;
4) preparation of metal layer/single-layer graphene film/metal substrate layer/single-layer graphene film/metal layer composite film
Processing the other side of the metal substrate layer of the metal layer/single-layer graphene film/metal substrate layer composite film by adopting the method in the step 1), and then repeating the operations in the steps 2) and 3) to prepare the metal layer/single-layer graphene film/metal substrate layer/single-layer graphene film/metal layer composite film.
Further, the specific operation of step 1) is as follows: mechanically polishing the surface of the metal substrate layer by using abrasive paper to remove most of an oxide layer on the surface, carrying out ultrasonic cleaning in acetone and absolute ethyl alcohol, then carrying out electrolytic polishing in a mixed solution of hydrofluoric acid, sulfuric acid and lactic acid, finally carrying out ultrasonic cleaning in deionized water, and drying by cold air for later use.
Further, the rapid transfer method comprises the steps of transferring the single-layer graphene film/polymethyl methacrylate film into deionized water, flatly covering the surface of the metal substrate layer subjected to surface treatment with the single-layer graphene film/polymethyl methacrylate film, drying at room temperature, and baking to remove residual water vapor to obtain the metal substrate layer/single-layer graphene film/polymethyl methacrylate film; and then, immersing the metal substrate layer/single-layer graphene film/polymethyl methacrylate film into acetone, after the polymethyl methacrylate film is completely dissolved, cleaning with ethanol, washing with deionized water, and drying to obtain the metal substrate layer loaded with the single-layer graphene film, namely the single-layer graphene film/metal substrate layer composite film.
And further, the deposition of the metal layer is to put the single-layer graphene film/metal substrate layer composite film into an ultrahigh vacuum chamber of a magnetron sputtering system, introduce high-purity argon after vacuumizing, deposit palladium by adopting a single target or co-deposit palladium-based metal alloy by adopting multiple targets, and obtain the metal layer/single-layer graphene film/metal substrate layer composite film with metal layers with different thicknesses by controlling the deposition time.
Use of a multilayer selective hydrogen permeation composite membrane for separating hydrogen from a gas mixture by selective diffusion.
Compared with the prior art, the invention has the following beneficial effects:
the multilayer selective hydrogen permeation composite membrane material can effectively prevent the high-temperature mutual diffusion of metal atoms in the metal layer and metal atoms (such as palladium atoms and niobium atoms) in the metal base material layer, does not influence the hydrogen permeation rate of the composite membrane, and prolongs the service life of the composite membrane. The multilayer selective hydrogen permeation composite membrane of the present invention is particularly useful for separating hydrogen from a gas mixture by selective diffusion.
Drawings
FIG. 1 is a schematic structural diagram of a Pd/Gr/Nb/Gr/Pd composite membrane;
FIG. 2 is an XPS spectrum of a niobium film after surface treatment, wherein a is the XPS spectrum of a niobium film after mechanical polishing and b is the XPS spectrum of a niobium film after electrolytic polishing;
FIG. 3 is a schematic diagram of a process for preparing a palladium film/single-layer graphene film/niobium film composite film by transfer and deposition;
FIG. 4 is a Raman spectrum before and after transferring a single-layer graphene film and depositing a palladium film, wherein a is a Nb film, b is a Nb/Gr/PMMA film, and c is a Nb/Gr film; d is a Pd/Gr/Nb/Gr/Pd composite membrane;
FIG. 5 is the surface interface micro-morphology and surface energy spectrum of Pd/Gr/Nb/Gr/Pd; wherein a-c is surface interface micro morphology, and d-g is surface energy spectrum;
FIG. 6 is SEM pictures of the surface of Pd/Nb/Pd and Pd/Gr/Nb/Gr/Pd composite membranes at different heat treatment temperatures, wherein a represents Pd/Nb/Pd, b represents Pd/Gr/Nb/Gr/Pd, and 1 represents no heat treatment; 2 represents 673K/3 h; 3 represents 773K/3 h; 4 represents 873K/3 h; 5 and 6 represent 973K/3 h;
FIG. 7 is XRD curves of Pd/Nb/Pd and Pd/Gr/Nb/Gr/Pd composite membranes at different heat treatment temperatures, wherein A represents Pd/Nb/Pd, B represents Pd/Gr/Nb/Gr/Pd, a represents no heat treatment, B represents 673K/3h, and c represents 773K/3 h; d represents 873K/3h, e represents 973K/3 h;
FIG. 8 is a Raman spectrum of a Pd/Gr/Nb/Gr/Pd composite membrane at different heat treatment temperatures, wherein a represents no heat treatment; b represents 673K/3h, c represents 773K/3h, d represents 873K/3h, and e represents 973K/3 h;
fig. 9 is the hydrogen permeability of nanocrystalline niobium, palladium/niobium/palladium, and palladium/single-layer graphene/niobium/single-layer graphene/palladium composite membranes.
Reference numerals: 1-palladium membrane, 2-single-layer graphene membrane and 3-niobium membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples the obtaining of the component materials
The niobium foil is selected from Alfa Aesar chemical Co., Ltd, has a purity of 99.8%, a thickness of 0.5mm, and a grain size of 50 to 150 μm and 20 to 100nm, respectively. The acetone and anhydrous ethanol are selected from chemical reagent factory of Syngnathus of Metrophytic department, and are analytically pure. The single-layer graphene film is selected from JCVSG-90-1/1-EX fast transfer graphene films of Nanjing Ginko nanometer materials GmbH. The palladium target, nickel palladium and ruthenium target are selected from Alfa Aesar chemical Co., Ltd, purity 99.99%, and scale phi 533mm 3 . All materials are put in a vacuum glove box and filled with inert gas for storage, so as to prevent oxidation and other impurities from being introduced.
Method for testing physical and chemical properties
SEM test
The microscopic morphologies of the surface and the interface of the niobium film and the palladium/niobium/palladium and palladium/single-layer graphene/niobium/single-layer graphene/palladium composite films before and after the heat treatment were characterized by a field emission scanning electron microscope (SEM, SIRION20, FEI corporation), and elemental scanning was performed by an attached X-ray energy spectrometer (EDS, YSTEM SIX).
XRD test
The crystal phase structure of the sample was analyzed using an X-ray diffractometer (XRD, test conditions are Cu target K α rays).
3. Raman spectroscopy
And (3) characterizing the Nb, Nb/Gr/PMMA, Nb/Gr and Nb/Gr/Pd/Gr/Nb composite membranes by adopting an In Via laser Raman spectrometer (Raman, Renishaw) with the wavelength of 532 nm. Scanning range: 4,000-500cm -1 。
XPS analysis
And analyzing the surface chemical states of the sample by adopting an X-ray photoelectron spectrometer (XPS), wherein the chemical states comprise surface element valences, element types and the like.
5. Testing of Hydrogen permeation Performance
And evaluating the hydrogen permeation performance of the composite membrane by adopting a hydrogen isotope gas phase driving permeation system. The diameter of the sample wafer is 11.9mm, and the effective permeation area is 24.63mm 2 The purity of deuterium gas is more than or equal to 99.999 percent.
Surface treatment of metal substrate layer
Adopt 500#, 1000#, 1500#, 2000# abrasive paper to carry out mechanical grinding to metal substrate layer surface to in proper order carry out ultrasonic cleaning with acetone, absolute ethyl alcohol, then get the metal substrate layer sample that the machinery ground the throwing and carry out electrochemical polishing, wherein direct current power supply is constant voltage 17V, and the mixed acid of adoption is hydrofluoric acid: concentrated sulfuric acid: lactic acid with the volume ratio of 1:3:6, a metal substrate layer needing electrochemical polishing is used as an anode, and a corrosion-resistant metal tungsten sheet is used as a cathode material. Because the mixed acid contains hydrofluoric acid which can etch glass, a polytetrafluoroethylene beaker is adopted as the container. The best removal effect can be achieved and the loss of the metal bulk material is minimum when the electrolytic polishing is carried out for 15 min. Taking out, ultrasonically cleaning with deionized water, and blow-drying with cold air for later use.
Transfer of single layer graphene films
Transferring the single-layer graphene film/polymethyl methacrylate film into deionized water, then clamping a metal substrate layer sample wafer by using forceps to enable the single-layer graphene film surface of the single-layer graphene film/polymethyl methacrylate film to flatly cover the surface of the metal substrate layer subjected to surface treatment, airing at room temperature for 24h, baking at 55 ℃ for 30min, and removing residual water vapor to obtain the metal substrate layer/single-layer graphene film/polymethyl methacrylate film; and then, immersing the metal substrate layer/single-layer graphene film/polymethyl methacrylate film into acetone for 10min, washing the film with ethanol after the polymethyl methacrylate film is completely dissolved, washing the film with deionized water, and drying the film to obtain the metal substrate layer loaded with the single-layer graphene film, namely the metal substrate layer/single-layer graphene film.
Preparation of metal substrate layer/single-layer graphene film/metal layer composite film
And sputtering a metal layer with the thickness of less than 200nm on the single-layer graphene film surface of the metal substrate layer/single-layer graphene film composite film by adopting a magnetron sputtering method to form the metal layer/single-layer graphene film/metal substrate layer composite film. The thickness of the metal layer is controlled by magnetron sputtering direct current voltage, current and time.
The preparation process comprises the following steps: placing the metal substrate layer/single-layer graphene film into an ultrahigh vacuum chamber of a magnetron sputtering system, and vacuumizing until the background vacuum of the chamber is better than 5 multiplied by 10 -6 Pa; and then introducing high-purity argon (Ar, 99.999%), performing single-target deposition of the palladium or multi-target co-deposition of the palladium-based metal alloy film when the argon flow is 21sccm, the self-bias voltage during deposition is 700V, the target sputtering power is 45W and the target-to-target distance is 8cm, and performing deposition for 15min to obtain the metal substrate layer/single-layer graphene film/metal layer composite film.
By adopting the process and the method, the following three composite films are respectively obtained:
example 1
The palladium membrane/single-layer graphene membrane/niobium membrane/single-layer graphene membrane/palladium membrane composite membrane is characterized in that the thickness of the niobium membrane is 0.3mm, the thickness of the palladium membrane is 100nm, and the thickness of the single-layer graphene membrane is 0.334 nm.
Mechanically polishing the surface of a nanocrystalline niobium film with the thickness of 0.3mm by using 500#, 1000#, 1500# and 2000# abrasive paper, and sequentially performing ultrasonic cleaning by using acetone and absolute ethyl alcohol; then, hydrofluoric acid is adopted: concentrated sulfuric acid: and carrying out electrolytic polishing on the mixed acid solution with the lactic acid volume ratio of 1:3:6, cleaning with deionized water, and drying with cold air for later use.
The surface of the niobium film after mechanical polishing and electrolytic polishing was analyzed by XPS, and as a result, as shown in fig. 2, it was found that electrolytic polishing was effective in removing the oxide layer on the surface of the niobium film.
Fig. 3 is a schematic diagram of a process for preparing a palladium film/single-layer graphene film/niobium film composite film by transfer and deposition. Transferring the single-layer graphene film/polymethyl methacrylate film (Gr/PMMA) into deionized water, clamping a niobium film (Nb) by using forceps, flatly covering the surface of the Gr/PMMA single-layer graphene film on the surface of the Nb film after surface treatment, airing at room temperature for 24h, baking at 55 ℃ for 30min, and removing residual water vapor to obtain the niobium/single-layer graphene film/polymethyl methacrylate film (Nb/Gr/PMMA); and then, soaking Nb/Gr/PMMA in acetone for 10min, after the PMMA is completely dissolved, cleaning with ethanol, washing with deionized water, and drying to obtain a niobium substrate layer loaded with the single-layer graphene film, namely the niobium/single-layer graphene film (Nb/Gr).
Placing the Nb/Gr film into an ultrahigh vacuum chamber of a magnetron sputtering system, and vacuumizing until the background vacuum of the chamber is better than 5 multiplied by 10 -6 Pa; and then introducing high-purity argon (Ar, 99.999 percent), depositing a palladium metal film when the argon flow is 21sccm, the self-bias voltage is 700V during deposition, the target sputtering power is 45W and the target base distance is 8cm, and depositing for 15min to obtain the palladium film/single-layer graphene film/niobium film composite film (Nb/Gr/Pd) with the palladium layer thickness of 100 nm.
Repeating the above operations, transferring the single-layer graphene film and depositing a palladium film on the other side of the niobium film to form a palladium film/single-layer graphene film/niobium film/single-layer graphene film/palladium film composite film, wherein the structure is shown in fig. 1.
Fig. 4 is a raman spectrum curve before and after transfer of a single-layer graphene film and deposition of a palladium film. The Raman spectrum characterization proves that the single-layer graphene film is not broken or has serious defects in the transfer and magnetron sputtering processes of the single-layer graphene film. FIG. 5 is the surface interface microscopic morphology and surface energy spectrum of Pd/Gr/Nb/Gr/Pd, and SEM morphology observation shows that the palladium membrane is flat and compact and is firmly bonded with the base material.
Example 2
The palladium ruthenium film/single-layer graphene film/niobium film/single-layer graphene film/palladium ruthenium film composite film is characterized in that the thickness of the niobium film is 0.3mm, the thickness of the palladium ruthenium film is 50nm, and the thickness of the single-layer graphene film is 0.334 nm.
Mechanically polishing the surface of a micron crystal niobium film with the thickness of 0.3mm by using 500#, 1000#, 1500# and 2000# abrasive paper, and sequentially carrying out ultrasonic cleaning by using acetone and absolute ethyl alcohol; then, hydrofluoric acid is adopted: concentrated sulfuric acid: and carrying out electrolytic polishing on the mixed acid solution with the lactic acid volume ratio of 1:3:6, cleaning with deionized water, and drying with cold air for later use.
Transferring the single-layer graphene film/polymethyl methacrylate film (Gr/PMMA) into deionized water, clamping a niobium film (Nb) by using forceps, flatly covering the surface of the Gr/PMMA single-layer graphene film on the surface of the Nb film after surface treatment, airing at room temperature for 24h, baking at 55 ℃ for 30min, and removing residual water vapor to obtain the niobium/single-layer graphene film/polymethyl methacrylate film (Nb/Gr/PMMA); and then, soaking Nb/Gr/PMMA in acetone for 10min, after the PMMA is completely dissolved, cleaning with ethanol, washing with deionized water, and drying to obtain a niobium substrate layer loaded with the single-layer graphene film, namely the niobium/single-layer graphene film (Nb/Gr).
Putting the Nb/Gr film into an ultrahigh vacuum chamber of a magnetron sputtering system, and vacuumizing until the background vacuum of the chamber is better than 5 multiplied by 10 -6 Pa; and then introducing high-purity argon (Ar, 99.999 percent), depositing a palladium-ruthenium metal alloy film by adopting a palladium and ruthenium dual target when the argon flow is 21sccm, the self bias voltage is 700V during deposition, the target sputtering power is 45W and the target base distance is 8cm, and depositing for 8min to obtain the palladium ruthenium film/single-layer graphene film/niobium film composite film (Nb/Gr/PdRu) with the palladium ruthenium layer thickness of 50 nm.
Repeating the operation, transferring the single-layer graphene film on the other surface of the niobium film and depositing the palladium ruthenium film to form the palladium ruthenium film/single-layer graphene film/niobium film/single-layer graphene film/palladium ruthenium film composite film.
Example 3
The palladium membrane/single-layer graphene membrane/niobium-titanium-nickel membrane/single-layer graphene membrane/palladium membrane composite membrane is characterized in that the thickness of the niobium-titanium-nickel membrane is 0.3mm, the thickness of the palladium membrane is 100nm, and the thickness of the single-layer graphene membrane is 0.334 nm.
Mechanically polishing the surface of a niobium-titanium-nickel alloy film with the thickness of 0.3mm by using 500#, 1000#, 1500# and 2000# abrasive paper, and sequentially carrying out ultrasonic cleaning by using acetone and absolute ethyl alcohol; then, hydrofluoric acid is adopted: concentrated sulfuric acid: and carrying out electrolytic polishing on the mixed acid solution with the lactic acid volume ratio of 1:3:6, cleaning the mixed acid solution with deionized water, and drying the mixed acid solution with cold air for later use.
Transferring the single-layer graphene film/polymethyl methacrylate film (Gr/PMMA) into deionized water, then clamping a niobium titanium nickel alloy film (Nb-Ti-Ni) by using forceps, flatly covering the surface of the Gr/PMMA single-layer graphene film on the surface of the Nb-Ti-Ni alloy film after surface treatment, airing at room temperature for 24h, baking at 55 ℃ for 30min, and removing residual water vapor to obtain the niobium titanium nickel/single-layer graphene film/polymethyl methacrylate film (Nb-Ti-Ni/Gr/PMMA); and then, soaking Nb-Ti-Ni/Gr/PMMA in acetone for 10min, after the PMMA is completely dissolved, cleaning with ethanol, washing with deionized water, and drying to obtain the niobium-titanium nickel layer loaded with the single-layer graphene film, namely the niobium-titanium nickel layer/single-layer graphene film (Nb-Ti-Ni/Gr).
Placing the Nb-Ti-Ni/Gr film into an ultrahigh vacuum chamber of a magnetron sputtering system, and vacuumizing until the background vacuum of the chamber is better than 5 multiplied by 10 -6 Pa; and then introducing high-purity argon (Ar, 99.999 percent), depositing a palladium metal film by adopting a palladium target when the argon flow is 21sccm, the self-bias voltage is 700V during deposition, the target sputtering power is 45W and the target base distance is 8cm, and depositing for 15min to obtain the palladium film/single-layer graphene film/niobium-titanium-nickel film composite film (Nb-Ti-Ni/Gr/Pd) with the palladium layer thickness of 100 nm.
Repeating the operation, transferring the single-layer graphene film and depositing a palladium film on the other side of the niobium-titanium-nickel film to form a palladium film/single-layer graphene film/niobium-titanium-nickel film/single-layer graphene film/palladium film composite film.
Comparative example 1
A niobium film, wherein the niobium film has a thickness of 0.3 mm.
Mechanically polishing the surface of a niobium film with the thickness of 0.3mm by using 500#, 1000#, 1500# and 2000# abrasive paper, and sequentially carrying out ultrasonic cleaning by using acetone and absolute ethyl alcohol; then, hydrofluoric acid is adopted: concentrated sulfuric acid: and carrying out electrolytic polishing on the mixed acid solution with the lactic acid volume ratio of 1:3:6, cleaning with deionized water, and drying with cold air for later use.
Comparative example 2
The palladium/niobium/palladium composite membrane has a niobium membrane thickness of 0.3mm and a palladium membrane thickness of 100 nm.
Mechanically polishing the surface of a niobium film with the thickness of 0.3mm by using 500#, 1000#, 1500# and 2000# abrasive paper, and sequentially carrying out ultrasonic cleaning by using acetone and absolute ethyl alcohol; then, hydrofluoric acid is adopted: concentrated sulfuric acid: and carrying out electrolytic polishing on the mixed acid solution with the lactic acid volume ratio of 1:3:6, cleaning the mixed acid solution with deionized water, and drying the mixed acid solution with cold air for later use.
And respectively sputtering a layer of palladium membrane with the thickness of 100nm on the two surfaces of the niobium membrane by adopting a magnetron sputtering method to form the palladium/niobium/palladium composite membrane.
Results and analysis
The composite membranes obtained in examples and comparative examples were subjected to a hydrogen permeation test, and the results thereof are shown in table 1.
Table 1 results of hydrogen permeation test of the composite membranes obtained in examples and comparative examples
As a result of analyzing the data shown in Table 1, it was found that the permeability of niobium metal itself to hydrogen was low, i.e., 6.25X 10 at 600 deg.C -10 mol·m -1 ·s -1 ·Pa -0.5 (comparative example 1) when a palladium membrane was deposited on the surface, the permeability was increased by about one order of magnitude (examples 1-3 and comparative example 2) to 10 -9 mol·m -1 ·s -1 ·Pa -0.5 And the infiltration temperature is reduced, which is beneficial to saving energy consumption.
Contrast the presence of a monolayer graphene interface resistanceIn the interlayer composite films (examples 1-3 and comparative example 2), it can be seen that there is no significant difference in hydrogen permeability between the two composite films before heat treatment, and the hydrogen permeability of the palladium/niobium/palladium composite film is significantly reduced after treatment at 450 ℃ for 24 hours (comparative example 2, 1.23 × 10) -11 mol·m -1 ·s -1 ·Pa -0.5 ) And as the heat treatment time is prolonged until no data can be obtained by tests, the palladium and niobium atoms are diffused mutually during the heat treatment process to form NbPd for preventing the hydrogen atoms from diffusing and permeating 3 Complex, which in turn results in a significant decrease in hydrogen permeability. When a single layer graphene film is introduced at the palladium/niobium interface, the graphene film is dense and has a low surface energy (4.67 x 10) -2 J/m 2 ) Therefore, palladium atoms hardly penetrate through the graphene film to perform mutual diffusion reaction with niobium atoms, and meanwhile, due to the proton penetration specificity of the graphene film, the diffusion and penetration of hydrogen atoms are ensured, so that the hydrogen permeability of the composite film is ensured.
In order to further verify whether the single-layer graphene film can block mutual diffusion of palladium and niobium atoms at high temperature, the palladium/niobium/palladium composite film (comparative example 2) and the palladium/single-layer graphene/niobium/single-layer graphene/palladium composite film (example 1) are subjected to heat treatment at 400-700 ℃ for 3 hours, and the surface morphology of the composite film is analyzed, as shown in fig. 6. The result shows that the Pd/Nb/Pd and Pd/Gr/Nb/Gr/Pd composite membranes gradually have dense and hemp-like pinhole-shaped holes on the surfaces along with the increase of the heat treatment temperature, and the holes are larger at higher temperature. When the temperature is continuously increased to 973K, the hole collapse appearance appears on the surface of the Pd/Nb/Pd composite membrane, and the holes of the palladium membrane on the surface of the Pd/Gr/Nb/Gr/Pd composite membrane melt and disappear, and are gathered together again to form an island-shaped structure appearance, which shows that the single-layer graphene membrane has the feasibility of preventing palladium atoms from penetrating through the graphene membrane to perform mutual diffusion reaction with niobium atoms.
XRD scans of the Pd/Nb/Pd and Pd/Gr/Nb/Gr/Pd composite membranes at different heat treatment temperatures are shown in FIG. 7. It can be found that, for the Pd/Nb/Pd composite membrane, when the Pd/Nb/Pd composite membrane is subjected to heat treatment for 3 hours at different temperatures, not only a characteristic absorption peak of Nb but also a characteristic absorption peak of Nb and Pd interdiffusion appear, which indicates that even if a hydrogen permeation experiment is carried out at a lower temperature (673K), niobium and palladium atoms are also likely to interdiffuse; at high temperature, the palladium film deposited on the surface of the niobium substrate has serious holes, so that the oxidation of the surface of the niobium film is further accelerated to form a compact oxide layer, and the hydrogen permeability is rapidly reduced. For the Pd/Gr/Nb/Gr/Pd composite membrane, due to the existence of the Gr membrane, no obvious hetero peak is observed in the composite membrane even if the composite membrane is subjected to heat treatment for 3 hours at 973K, which indicates that the graphene membrane has the function of blocking palladium and niobium from mutual diffusion below 973K.
FIG. 8 shows the Raman curves of the Pd/Gr/Nb/Gr/Pd composite membrane at different heat treatment temperatures. It can be seen that 1597cm before and after heat treatment -1 And 2478cm -1 Characteristic absorption peaks corresponding to a G band and a 2D band of the single-layer graphene film appear at the same time, which shows that the graphene film with an sp2 hybrid structure still exists after heat treatment, but the strength of the characteristic absorption peak of the 2D band is obviously reduced; correspondingly, at 1350cm -1 The characteristic absorption peak corresponding to the graphene D band appears, and the higher the temperature is, the higher the intensity of the absorption peak of the D band is, which shows that in the heat treatment process, along with the micro deformation of the niobium film and the palladium film, the carbon six-membered ring structure of the graphene film is damaged under the stress action, so that the structural defect is generated, and the higher the temperature is, the more the defects are generated. When the temperature reaches 973K, 1350cm -1 The characteristic absorption peak of (b) disappears, which indicates that the graphene film has the function of blocking mutual diffusion of palladium and niobium atoms below 873K. The Pd/Nb/Pd and Pd/Gr/Nb/Gr/Pd composite membranes are prepared by taking the nanocrystalline niobium membrane as a substrate, and the hydrogen permeability of the composite membranes is examined (figure 9), and the hydrogen permeability of the Pd/Nb/Pd composite membrane is found to be in a serious reduction trend below 773K, while the Pd/Gr/Nb/Gr/Pd composite membrane still maintains higher hydrogen permeability. When the temperature is too high (873K), a slight decrease in hydrogen permeability occurs, which may be caused by a defect in the monolayer graphene film due to the deformation of the niobium film.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A multilayer selective hydrogen permeation composite membrane is characterized by comprising a metal substrate layer with high hydrogen permeability, a metal layer with catalytic activity and permeability to hydrogen and a single-layer graphene membrane with selective permeability to proton hydrogen; the metal base material layer is niobium or a metal alloy consisting of niobium and other metal elements, the metal layer is palladium or a metal alloy consisting of palladium and other elements, and the metal base material layer, the single-layer graphene film and the metal layer are sequentially and tightly attached.
2. The multilayer selective hydrogen permeation composite membrane according to claim 1, wherein the composite membrane is in the order of a metal layer, a single-layer graphene membrane, a metal substrate layer, a single-layer graphene membrane, and a metal layer.
3. The multilayer selective hydrogen permeation composite membrane according to claim 1 or 2, wherein the metal substrate layer is niobium or a metal alloy of niobium and one or more of titanium, nickel, tantalum, zirconium, hafnium and cobalt metal elements.
4. The multilayer selective hydrogen permeation composite membrane according to claim 1 or 2, wherein the crystal morphology of the metal substrate layer is any one of single crystal, nano crystal or micro crystal, and the crystal grain size of the metal substrate layer is 20nm to 200 μm.
5. The multilayer selective hydrogen permeation composite membrane according to claim 1 or 2, wherein the metal layer is a continuous or discontinuous metal alloy film composed of palladium or palladium and nickel, ruthenium, copper elements, and has a thickness of less than 200 nm.
6. A method of producing a multilayer selective hydrogen permeation composite membrane according to claim 1 or 2, comprising the steps of:
1) surface treatment of metal substrate layer
Removing most of an oxide layer on the surface of the metal substrate layer, and then carrying out cold air blow drying for later use after electrolytic polishing and ultrasonic cleaning;
2) transfer of single layer graphene films
Transferring the prefabricated single-layer graphene film to the surface of the metal base material layer after surface treatment by adopting a rapid transfer method to prepare a single-layer graphene film/metal base material layer composite film;
3) deposition of metal layers
Sputtering a layer of metal film on the single-layer graphene film surface of the single-layer graphene film/metal base material layer composite film by adopting a magnetron sputtering method to form a metal layer/single-layer graphene film/metal base material layer composite film;
4) preparation of metal layer/single-layer graphene film/metal substrate layer/single-layer graphene film/metal layer composite film
Processing the other side of the metal substrate layer of the metal layer/single-layer graphene film/metal substrate layer composite film by adopting the method in the step 1), and then repeating the operations in the steps 2) and 3) to prepare the metal layer/single-layer graphene film/metal substrate layer/single-layer graphene film/metal layer composite film.
7. A method for preparing a multilayer selective hydrogen permeation composite membrane according to claim 6, wherein the specific operation of step 1) is: mechanically polishing the surface of the metal substrate layer by using abrasive paper to remove most of an oxide layer on the surface, carrying out ultrasonic cleaning in acetone and absolute ethyl alcohol, then carrying out electrolytic polishing in a mixed solution of hydrofluoric acid, sulfuric acid and lactic acid, finally carrying out ultrasonic cleaning in deionized water, and drying by cold air for later use.
8. The method for preparing the multilayer selective hydrogen permeation composite membrane according to claim 6, wherein the rapid transfer method comprises the steps of transferring the single-layer graphene membrane/polymethyl methacrylate membrane into deionized water, flatly covering the single-layer graphene membrane/polymethyl methacrylate membrane on the surface of the metal base material layer after surface treatment, airing at room temperature, and baking to remove residual water vapor to obtain the metal base material layer/single-layer graphene membrane/polymethyl methacrylate membrane; and then immersing the metal substrate layer/single-layer graphene film/polymethyl methacrylate film into acetone, after the polymethyl methacrylate film is completely dissolved, cleaning with ethanol, washing with deionized water, and drying to obtain the metal substrate layer loaded with the single-layer graphene film, namely the single-layer graphene film/metal substrate layer composite film.
9. The method for preparing the multilayer selective hydrogen permeation composite membrane according to claim 6, wherein the metal layer is deposited by placing the single-layer graphene membrane/metal substrate layer composite membrane into an ultrahigh vacuum chamber of a magnetron sputtering system, introducing high-purity argon after vacuumizing, depositing palladium by using a single target or co-depositing a palladium-based metal alloy by using multiple targets, and controlling the deposition time to obtain the metal layer/single-layer graphene membrane/metal substrate layer composite membrane with metal layers of different thicknesses.
10. Use of a multilayer selective hydrogen permeation composite membrane according to claim 1 or 2, for separating hydrogen from a gas mixture by selective diffusion.
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