CN113846289A - Method for preparing layered double-hydroxide film based on co-sputtering intermediate film in-situ conversion - Google Patents
Method for preparing layered double-hydroxide film based on co-sputtering intermediate film in-situ conversion Download PDFInfo
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- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
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- 238000004140 cleaning Methods 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
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- 239000000243 solution Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
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- 229910045601 alloy Inorganic materials 0.000 claims description 9
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
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- 239000007769 metal material Substances 0.000 claims description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
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- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present disclosure provides a method for preparing a layered double hydroxide metal hydroxide (LDH) membrane based on co-sputtering intermediate membrane in-situ conversion, comprising the steps of: s1, co-depositing two or more metals on the surface of the substrate material by utilizing a co-sputtering technology to obtain a co-sputtered intermediate film; and S2, carrying out in-situ conversion on the co-sputtered intermediate film through a hydrothermal reaction process to realize hydroxylation, and obtaining the dihydroxy metal hydroxide film. The method provided by the disclosure gets rid of the problem that the traditional in-situ LDH surface membrane is limited by the substrate, and can realize the conversion preparation of the in-situ LDH membrane on substrates with different sizes, shapes and materials; and the in-situ growth of the LDH membrane with controllable thickness can be simply and efficiently realized.
Description
Technical Field
The disclosure relates to the technical field of surfaces, in particular to a method for preparing a layered double hydroxide film based on co-sputtering intermediate film in-situ conversion.
Background
The Layered Double Hydroxide (LDH) is a hydrotalcite-like two-dimensional layered nano material with the general formula [ M2 + 1-xM3+ x(OH)2]x+[An-]x/n·mH2O, wherein M2+And M3+Denotes a divalent and trivalent metal cation, An-Is an interlayer anion. The unique layered structure and the diverse chemical compositions endow the LDH material with excellent nano-storage property, catalytic property, corrosion resistance, self-healing property and the like, and the characteristics cause the LDH material to draw wide attention and application in the fields of energy storage, catalysis, corrosion resistance, environment, biomedicine and the like.
In the application of the fields of catalysis, corrosion prevention, environment and the like, the LDH material is required to be attached to the surface of a substrate material in the form of a surface membrane, so that the preparation of the in-situ LDH membrane has important application and development prospects in recent years. Whereas a typical in situ LDH conversion membrane process typically soaks a metal (M1) substrate material in another metal (M2) salt solution, dissolving or forming hydroxides of the M1 substrate to provide a source of M1 metal, the M2 metal salt acts as another necessary metal cation for the formation of the LDH membrane. However, this method is severely limited by the substrate material, and the preparation of in-situ LDH membranes on some metal or non-metal surfaces is still very difficult. On the other hand, the hydrothermal growth process is influenced by a plurality of parameters, and the regulation and control of the process are particularly complicated, so that the controllable growth of the in-situ LDH membrane is difficult to realize, and particularly the large-thickness in-situ LDH membrane is difficult to obtain.
Disclosure of Invention
In view of the problems existing in the background art, the present disclosure aims to provide a method for preparing a layered double hydroxide membrane (LDH membrane) based on in-situ conversion of a co-sputtered intermediate membrane, which is simple, easy to control, efficient and not limited by a substrate material, so as to get rid of the problem that the conventional in-situ LDH surface membrane is limited by the substrate, realize the preparation of the in-situ LDH membrane on substrates with different sizes, shapes and materials, and get rid of the process bottleneck for large-scale industrial production and application of the LDH surface membrane.
The method for preparing the layered double hydroxide film based on the co-sputtering intermediate film in-situ conversion comprises the following steps: s1, co-depositing two or more metals on the surface of the substrate material by utilizing a co-sputtering technology to obtain a co-sputtered intermediate film; and S2, carrying out in-situ conversion on the co-sputtered intermediate film through a hydrothermal reaction process to realize hydroxylation, and obtaining the dihydroxy metal hydroxide film.
In some embodiments, the base material comprises at least one of a metal base, a non-metal base; wherein the metal substrate comprises at least one of magnesium and its alloy, aluminum and its alloy, zinc and its alloy; the non-metal substrate comprises at least one of glass sheets, cotton cloth, foamed nickel and foamed copper.
In some embodiments, the substrate material is pretreated; wherein the pretreatment of the metal substrate material comprises mechanical grinding and polishing of the metal material; and/or the pretreatment of the non-metal substrate material comprises ultrasonic cleaning by absolute ethyl alcohol, cleaning by deionized water and drying.
In some embodiments, the co-sputtered intermediate film obtained in step S1 includes at least one of a zinc-aluminum co-sputtered film, a magnesium-aluminum co-sputtered film, and a magnesium-zinc-aluminum co-sputtered film.
In some embodiments, the zinc sputtering power is 30W to 100W during the co-sputtering deposition; and/or the magnesium sputtering power is 50W-100W; and/or the aluminum sputtering power is 50W-200W.
In some embodiments, step S1 may be: placing the substrate material on a sputtering platform of a magnetron sputtering system, and making the vacuum degree of a cavity be 7.8 multiplied by 10 through a vacuum pumping process-4Continuously introducing argon into the cavity under Pa to stabilize the pressure of the argon within 0.2-0.6 Pa, and realizing the preparation of the co-sputtering intermediate film; wherein the distance between the target material and the substrate material is 60mm-80mm, the ambient temperature is 25 +/-2 ℃, and the sputtering time is 5 min-180 min.
In some embodiments, the hydrothermal solution of the hydrothermal reaction is adjusted to a pH of 4 to 10.
In some embodiments, the hydrothermal temperature of the hydrothermal reaction process is 60 ℃ to 100 ℃.
In some embodiments, the hydrothermal reaction process has a hydrothermal time of 2h to 72 h.
In some embodiments, step S2 may be: placing the co-sputtered intermediate film sample obtained in the step S1 in an aqueous solution with the pH of 4-10, and vertically placing the sample in a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction; and after the reaction is finished, taking out the sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying to obtain the dihydroxy metal hydroxide membrane.
The present disclosure includes at least the following advantageous effects:
according to the preparation process of the LDH surface membrane, the co-sputtering intermediate membrane is introduced, the intermediate membrane can provide metal ions for synthesis of the LDH membrane, the co-sputtering intermediate membrane can be subjected to a stimulation reaction on the co-sputtering membrane under a certain condition, the total in-situ conversion from the co-sputtering intermediate membrane to the LDH membrane is realized, and the LDH membranes on different substrates can be prepared by introducing the intermediate membrane. The thickness control of the co-sputtered film can be realized by simply regulating and controlling parameters, and then the co-sputtered intermediate film is completely converted in situ;
therefore, the method provided by the disclosure can realize the thickness-controllable growth of the LDH membrane, particularly, the problem of insufficient raw material supply of the substrate material in the hydrothermal process is solved through the conversion of the intermediate membrane, the growth of the LDH membrane is not limited, the preparation of the large-thickness in-situ LDH membrane is realized, the requirements of various functional characteristics such as science and technology, industry and the like are further met, and the application range of the LDH surface membrane is expanded.
Drawings
Figure 1 is a microscopic topography of the zinc-aluminum LDH surface film prepared on the glass sheet of example 1.
Figure 2 is an XRD pattern of the co-sputtered interlayer film and zinc-aluminum LDH surface film prepared on the glass sheet of example 1.
Figure 3 is a microscopic cross-sectional view of the zinc-aluminum LDH surface membrane prepared in example 2.
Figure 4 is a microscopic cross-sectional view of the zinc-aluminum LDH surface membrane prepared in example 3.
Fig. 5 is a surface topography of the zinc-aluminum LDH surface film prepared on cotton cloth in example 4.
Fig. 6 is a surface topography of the magnesium aluminum LDH surface film prepared on the magnesium alloy of example 5.
Detailed Description
It is to be understood that the disclosed embodiments are merely exemplary of the disclosure that may be embodied in various forms, and that specific details of the disclosure are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the disclosure. In the description of the present disclosure, co-sputtering techniques are well known to those skilled in the art, and the co-sputtering systems (or apparatus, devices, methods, etc.) employed are familiar to those skilled in the art and can be operated by those skilled in the art; the terms "binary" metal, "ternary" metal refer to two different metals, three different metals, respectively; the term "co-deposition" refers to co-deposition simultaneously, not in sequential order. "target" refers to a sputtering source that forms various functional films on a substrate by sputtering under suitable process conditions with a magnetron sputtering or other type of coating system. In the description of the present disclosure, terms and terms not specifically described are common general knowledge of those skilled in the art, and methods not specifically described are conventional methods known to those skilled in the art.
The method of the present disclosure for preparing a layered double hydroxide membrane (abbreviated as LDH membrane throughout the present disclosure) based on co-sputtering intermediate membrane in situ conversion is described next.
In order to realize the growth process of an in-situ LDH membrane in a simple, efficient and pollution-free manner, solve the problem that the growth of the LDH membrane is limited by a substrate and realize the controllable growth of the LDH membrane, the disclosure provides a method for preparing the LDH membrane by introducing a co-sputtering intermediate membrane through in-situ conversion.
The method for preparing the layered double hydroxide film based on in-situ conversion of the co-sputtered intermediate film comprises the following steps: s1, co-depositing two or more metals on the surface of the substrate material by utilizing a co-sputtering technology to obtain a co-sputtered intermediate film; and S2, carrying out in-situ conversion on the co-sputtered intermediate film through a hydrothermal reaction process to realize hydroxylation, and obtaining the dihydroxy metal hydroxide film.
[ step S1]
In the preparation of the intermediate film in step S1 of the present disclosure, the co-sputtering technique may be a magnetron sputtering co-sputtering technique, which is a green, simple and not limited by the substrate material, and can implement the deposition process of any shape, size and material substrate surface, and can implement the co-sputtering intermediate film of two or even more metals by selecting different targets. In addition, the co-sputtering intermediate film with controllable metal proportion and controllable thickness can be realized by simply regulating and controlling the sputtering parameters, and sufficient favorable factors are provided for the subsequent realization of the controllable conversion of the LDH film.
In some embodiments, the base material comprises at least one of a metallic base, a non-metallic base; wherein, in some embodiments, the metal substrate comprises at least one of magnesium and alloys thereof, aluminum and alloys thereof, zinc and alloys thereof; the non-metallic substrate comprises at least one of glass flakes, cotton cloth, nickel foam, copper foam.
In some embodiments, the substrate material may be pretreated. In some embodiments, the pre-treatment of the metal base material comprises mechanically grinding, polishing the metal material; in some embodiments, the mechanical grinding uses 400-mesh, 800-mesh, 1200-mesh and 2000-mesh SiC aqueous sandpaper to grind and polish the metal surface. In some embodiments, the pre-treatment of the non-metallic material substrate comprises cleaning, degreasing the surface thereof; in some embodiments, the surface cleaning degreasing process may be performed by ultrasonic cleaning of the non-metallic material substrate with absolute ethanol and deionized water, for example: ultrasonically cleaning the non-metal material substrate for 15min by using absolute ethyl alcohol, then ultrasonically cleaning the non-metal material substrate for 10min by using deionized water, taking out a sample, and drying the sample for later use.
In step S1 of the present disclosure, the intermediate film is obtained by co-sputtering co-deposition of metal on the surface of the substrate material to provide a metal source for the conversion of the LDH film. In some embodiments, the co-sputtered intermediate film comprises a binary metal and/or a ternary metal, for example, at least one of a zinc-aluminum co-sputtered film, a magnesium-zinc-aluminum co-sputtered film. In some embodiments, the sputtering power of the magnesium metal is 50W-100W; in some embodiments, the sputtering power of the metal zinc is 30W-100W; in some embodiments, the sputtering power of the metal aluminum is 50W-200W; in some embodiments, the sputtering time is from 5min to 180 min.
In some embodiments, the co-sputtering pressure is 0.2Pa to 0.6 Pa.
In some embodiments, step S1 may be: placing the substrate material on a sputtering platform of a magnetron sputtering system, and making the vacuum degree of a cavity be 7.8 multiplied by 10 through a vacuum pumping process-4Continuously introducing argon into the cavity under Pa to stabilize the pressure between 0.2Pa and 0.6Pa, so as to realize the preparation of the co-sputtering intermediate film; wherein the distance between the target material and the substrate material is 60mm-80mm, the environmental temperature is 25 +/-2 ℃, and the sputtering time is 5 min-180 min.
[ step S2]
The intermediate membrane obtained in step S1 can provide a divalent and trivalent metal source (such as magnesium, aluminum or zinc) for the growth conversion of the LDH membrane. Under certain pH conditions, metals (such as magnesium, aluminum or zinc) can release ions or form hydroxides, and the direct conversion of the LDH membrane is possible under the mild condition without introducing any additional metal ions.
Among them, the pH value in the hydrothermal process of step S2 is an important parameter for the formation conversion process of the LDH membrane. In some embodiments, the present disclosure can create an acidic environment for a hydrothermal solution by dilute nitric acid, and simultaneously introduce nitrate anions during the preparation of an LDH membrane, so that LDH-NO can be realized in one step3 -And (3) preparing a film. In some embodiments, LDH-OH can be achieved simultaneously by creating an alkaline environment for the hydrothermal solution with a sodium hydroxide solution-And (5) growing the film. In some embodiments, the hydrothermal solution of the hydrothermal reaction is adjusted to a pH of 4 to 10.
Meanwhile, the hydrothermal temperature and the hydrothermal time are two other important factors of the LDH membrane conversion process, and the uniform and compact LDH membrane conversion process is realized by adjusting the temperature and the hydrothermal time. In some embodiments, the hydrothermal temperature of the hydrothermal reaction process is 60 ℃ to 100 ℃. In some embodiments, the hydrothermal reaction process has a hydrothermal time of 2h to 72 h.
In some embodiments, step S2 may be: placing the co-sputtered intermediate film sample obtained in the step S1 in an aqueous solution with the pH of 4-10, and vertically placing the sample in a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction; after the reaction is finished, taking out a sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying to obtain a dihydroxy metal hydroxide membrane; in some embodiments, drying may be by drying in an oven or blow drying with cold air.
The disclosure is further illustrated with reference to the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. In the following examples and comparative examples, reagents, materials and instruments used were commercially available or prepared by methods known in the art, unless otherwise specified.
Example 1
S0, pretreatment of the substrate material: and ultrasonically cleaning the glass sheet for 15min by using absolute ethyl alcohol, ultrasonically cleaning the glass sheet for 10min by using deionized water, and taking out a sample and drying the sample.
S1, co-sputtering intermediate film preparation: placing the processed glass substrate on a sputtering platform of a magnetron sputtering system, and vacuumizing to ensure that the vacuum degree of a cavity is 7.8 multiplied by 10-4And continuously introducing argon into the cavity under Pa to stabilize the pressure of the cavity at 0.4Pa, and preparing the zinc-aluminum co-sputtering intermediate film by adopting a zinc-aluminum co-sputtering technology, wherein the sputtering power of zinc is 40W, the sputtering power of aluminum is 100W, the distance between the target and the substrate material is 60m, the ambient temperature is 25 +/-2 ℃, and the sputtering time is 60 min.
S2, in situ conversion of LDH membrane: and (3) placing the sample on which the zinc-aluminum co-sputtering film is deposited into a sodium hydroxide solution with the pH value of 8, and vertically placing the sample in a PTFE (polytetrafluoroethylene) hydrothermal reaction kettle for hydrothermal reaction. And after the reaction is finished, taking out a sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying the sample in an oven or drying the sample by using cold air to obtain the zinc-aluminum LDH membrane sample.
Example 2
S0, pretreatment of the substrate material: ultrasonically cleaning the glass sheet for 15min by using absolute ethyl alcohol, ultrasonically cleaning the glass sheet for 10min by using deionized water, and taking out a sample and drying the sample.
S1, co-sputtering intermediate film preparation: placing the processed glass sheet on a shooting table of a magnetron sputtering system, and ensuring the vacuum degree of a cavity to be 7.8 multiplied by 10 through a vacuum pumping process-4The content of the compound is less than Pa,and continuously introducing argon into the cavity to stabilize the pressure of the cavity to be 0.2Pa, and realizing the preparation of the zinc-aluminum co-sputtering intermediate film by adopting a co-sputtering technology. Wherein the sputtering power of zinc is 30W, the sputtering power of aluminum is 100W, the distance between the target and the substrate material is 80m, the ambient temperature is 25 +/-2 ℃, and the sputtering time is 5 min.
S2, in situ conversion of LDH membrane: and (3) placing the sample on which the zinc-aluminum co-sputtering film is deposited into a sodium hydroxide solution with the pH value of 9, and vertically placing the sample in a PTFE (polytetrafluoroethylene) hydrothermal reaction kettle for hydrothermal reaction. And after the reaction is finished, taking out the sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying the sample in an oven or drying the sample by using cold air to obtain the zinc-aluminum LDH membrane sample.
Example 3
S0, pretreatment of the substrate material: ultrasonically cleaning the glass sheet for 15min by using an absolute ethyl alcohol solution, ultrasonically cleaning the glass sheet for 10min by using deionized water, and taking out a sample and then drying the sample.
S1, co-sputtering intermediate film preparation: placing the processed glass sheet on a shooting table of a magnetron sputtering system, and ensuring the vacuum degree of a cavity to be 7.8 multiplied by 10 through a vacuum pumping process-4And continuously introducing argon into the cavity below Pa to stabilize the pressure of the cavity to be 0.2Pa, and realizing the preparation of the zinc-aluminum co-sputtering intermediate film by adopting a co-sputtering technology. Wherein the sputtering power of zinc is 50W, the sputtering power of aluminum is 100W, the distance between the target and the substrate material is 70m, and the ambient temperature is 25 +/-2 ℃. The sputtering time was 90 min.
S2, in situ conversion of zinc aluminum LDH membrane: and (3) placing the sample on which the zinc-aluminum co-sputtering film is deposited into a sodium hydroxide solution with the pH value of 9, and vertically placing the sample in a PTFE (polytetrafluoroethylene) hydrothermal reaction kettle for hydrothermal reaction. And after the reaction is finished, taking out the sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying the sample in an oven or drying the sample by using cold air to obtain the zinc-aluminum LDH membrane sample.
Example 4
S0, pretreatment of the substrate material: ultrasonically cleaning the cotton cloth material for 15min by using an absolute ethyl alcohol solution, ultrasonically cleaning the cotton cloth material for 10min by using deionized water, and taking out a sample and then drying the sample.
S1, co-sputtering intermediate film preparation: placing the treated cotton cloth on a sputtering table of a magnetron sputtering system, and vacuumizing to make the vacuum degree of the cavity 7.8 × 10-4And continuously introducing argon into the cavity below Pa to stabilize the pressure of the cavity to be 0.4Pa, and realizing the preparation of the zinc-aluminum co-sputtering intermediate film by adopting a co-sputtering technology. Wherein the sputtering power of zinc is 40W, the sputtering power of aluminum is 80W, the distance between the target and the substrate material is 70m, the ambient temperature is 25 +/-2 ℃, and the sputtering time is 30 min.
S2, in situ conversion of LDH membrane: and (3) placing the sample on which the zinc-aluminum co-sputtering film is deposited into a sodium hydroxide aqueous solution with the pH value of 8, and vertically placing the sample in a PTFE (polytetrafluoroethylene) hydrothermal reaction kettle for hydrothermal reaction. And after the reaction is finished, taking out the sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying the sample in an oven or drying the sample by using cold air to obtain the zinc-aluminum LDH membrane sample.
Example 5
S0, pretreatment of the substrate material: and (3) grinding and polishing the magnesium alloy sample by using 400-mesh, 800-mesh, 1200-mesh and 2000-mesh SiC water-based sand paper respectively. And then ultrasonically cleaning the material for 15min by using absolute ethyl alcohol, ultrasonically cleaning the material for 10min by using deionized water, taking out the sample, and drying the sample by using cold air for later use.
S1, co-sputtering intermediate film preparation: placing the processed magnesium alloy substrate on a sputtering platform of a magnetron sputtering system, and ensuring the vacuum degree of a cavity to be 7.8 multiplied by 10 through a vacuum pumping process-4And continuously introducing argon into the cavity below Pa to stabilize the pressure of the cavity to be 0.2Pa, and realizing the preparation of the magnesium-aluminum co-sputtering intermediate film by adopting a co-sputtering technology. Wherein the sputtering power of magnesium is 60W, the sputtering power of aluminum is 90W, the distance between the target and the substrate material is 70mm, the ambient temperature is 25 +/-2 ℃, and the sputtering time is 50 min.
S2, in situ conversion of LDH membrane: and (3) placing the sample on which the magnesium-aluminum co-sputtering film is deposited in a nitric acid solution with the pH value of 4, and vertically placing the sample in a PTFE (polytetrafluoroethylene) hydrothermal reaction kettle for hydrothermal reaction. And after the reaction is finished, taking out a sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying the sample in an oven or blowing the sample by using cold air to obtain the magnesium-aluminum LDH membrane sample.
FIG. 1 is a microscopic morphology of the zinc-aluminum LDH surface membrane prepared in example 1, from which it can be observed that the lamellar LDH structure uniformly covers the surface of the substrate, and the size distribution of the lamellar structure is between 500nm and 3 μm.
Fig. 2 shows XRD patterns of the Zn-Al co-sputtered film and the Zn-Al LDH surface film in example 1, and from the XRD crystal form results, it is found that the co-sputtered film corresponds to characteristic peaks of Zn (002), Zn (100), Zn (101), Zn (102), Zn (103), and Zn (110) at 2 θ of 36.3 °, 39.1 °, 43.2 °, 54.3 °, 70.1 °, and 70.7 °, respectively, and also corresponds to characteristic peaks of Al (111), Al (200), and Al (220) at 2 θ of 38.6 °, 44.9 °, and 65.4 °. The zinc-aluminum LDH surface membrane forms characteristic peaks (003), (006) and (012) of a typical LDH layered structure at 11.7 degrees, 23.6 degrees and 32.5 degrees, and an intercalation anion is OH-Indicating that the intermediate membrane has been successfully converted to an LDH membrane.
Figure 3 is a microscopic cross-sectional view of the zinc-aluminium LDH membrane prepared in example 2, from which it can be observed that the LDH membrane has a thickness of 2 μm.
Figure 4 is a microscopic cross-sectional view of the zinc aluminium LDH membrane prepared on the surface of the glass sheets in example 3, from which it can be observed that the LDH membrane can reach a thickness of 13 μm, with the lower part of the membrane having a smaller sheet structure size, a uniform and dense overall structure, and the sheet structure on the surface of the membrane having a larger size. As can be seen from the embodiment 2 and the embodiment 3, the thickness of the co-sputtering film can be controlled by regulating and controlling the magnetron sputtering parameters, and then the hydrothermal conversion process is regulated to completely convert the intermediate film, so that the growth of the LDH film with controllable thickness can be realized, and the problem that the existing LDH film with large thickness is difficult to realize can be solved.
Figure 5 is a surface microtopography of the LDH membrane prepared in example 4 on a cotton cloth substrate. It can be observed from the figure that the woven cotton cloth is evenly covered with a large number of nano-micron layered structures. This example illustrates that the method provided by the present disclosure can not only realize the in-situ growth of the LDH film on the substrate of magnesium alloy, aluminum alloy, etc. in the conventional sense, but also realize the in-situ growth of the LDH film on non-metals such as glass and cloth.
Fig. 6 is a surface topography of the magnesium aluminum LDH membrane prepared on the magnesium alloy substrate in example 5, from which it can be observed that a large number of nanosheet structures uniformly cover the surface. Magnesium-aluminum metal raw materials required by LDH growth are introduced by utilizing a co-sputtering technology, the in-situ growth process of various LDH surface membranes can be realized through the conversion of a hydrothermal process, an acid environment is provided for a hydrothermal solution through dilute nitric acid, and nitrate directly introduced can realize an LDH structure of nitrate anion intercalation in one step.
The above description is only exemplary of the present disclosure and should not be taken as limiting the present disclosure in any way, and although the present disclosure has been described in terms of preferred embodiments, it is not intended to limit the present disclosure, and those skilled in the art can make modifications and equivalents without departing from the scope of the present disclosure.
Claims (10)
1. A method for preparing a layered double hydroxide film based on co-sputtering intermediate film in-situ conversion is characterized by comprising the following steps:
s1: co-depositing two or more metals on the surface of the substrate material by utilizing a co-sputtering technology to obtain a co-sputtered intermediate film;
s2: and then, carrying out in-situ conversion on the co-sputtered intermediate film through a hydrothermal reaction process to realize hydroxylation, thereby obtaining the dihydroxy metal hydroxide film.
2. The method for preparing the layered double hydroxide film based on the co-sputtering intermediate film in-situ conversion according to claim 1, wherein the substrate material comprises at least one of a metal substrate and a non-metal substrate; wherein,
the metal substrate comprises at least one of magnesium and alloy thereof, aluminum and alloy thereof, zinc and alloy thereof; the non-metal substrate comprises at least one of glass sheets, cotton cloth, foamed nickel and foamed copper.
3. The method for preparing the layered double hydroxide film based on the co-sputtering intermediate film in-situ conversion according to claim 2, characterized in that a base material is pretreated; wherein the pretreatment of the metal substrate material comprises mechanical grinding and polishing of the metal material; and/or
The pretreatment of the non-metal substrate material comprises ultrasonic cleaning by absolute ethyl alcohol, cleaning by deionized water and drying.
4. The method for preparing the layered double hydroxide film based on the co-sputtering intermediate film in-situ conversion is characterized in that the co-sputtering intermediate film obtained in the step S1 comprises at least one of a zinc-aluminum co-sputtering film, a magnesium-aluminum co-sputtering film and a magnesium-zinc-aluminum co-sputtering film.
5. The method for preparing a layered double hydroxide film based on co-sputtering intermediate film in-situ conversion according to claim 2, characterized in that during co-sputtering deposition:
the zinc sputtering power is 30W-100W; and/or
The magnesium sputtering power is 50W-100W; and/or
The aluminum sputtering power is 50W-200W.
6. The method for preparing a layered double hydroxide film based on co-sputtering intermediate film in-situ conversion according to claim 1, wherein step S1 is:
placing the substrate material on a sputtering platform of a magnetron sputtering system, and making the vacuum degree of a cavity be 7.8 multiplied by 10 through a vacuum pumping process-4Continuously introducing argon into the cavity under Pa to stabilize the pressure of the argon within 0.2-0.6 Pa, and realizing the preparation of the co-sputtering intermediate film; wherein the distance between the target material and the substrate material is 60mm-80mm, the environmental temperature is 25 +/-2 ℃, and the sputtering time is 5 min-180 min.
7. The method for preparing the layered double hydroxide film based on the in-situ conversion of the co-sputtered intermediate film according to claim 1, wherein the pH of the hydrothermal solution of the hydrothermal reaction is adjusted to 4-10.
8. The method for preparing the layered double hydroxide film based on the in-situ conversion of the co-sputtered intermediate film according to claim 1, wherein the hydrothermal temperature of the hydrothermal reaction process is 60-100 ℃.
9. The method for preparing the layered double hydroxide film based on the in-situ conversion of the co-sputtered intermediate film as claimed in claim 1, wherein the hydrothermal reaction process has a hydrothermal time of 2-72 h.
10. The method for preparing a layered double hydroxide film based on co-sputtering intermediate film in-situ conversion according to claim 1, wherein step S2 is:
placing the co-sputtered intermediate film sample obtained in the step S1 in an aqueous solution with the pH of 4-10, and vertically placing the sample in a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction; and after the reaction is finished, taking out the sample, washing the sample by using deionized water and absolute ethyl alcohol, and drying to obtain the dihydroxy metal hydroxide membrane.
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| PCT/CN2021/129240 WO2023045042A1 (en) | 2021-09-24 | 2021-11-08 | Method for preparing layered double hydroxide film on the basis of in situ conversion of co-sputtering intermediate film |
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|---|---|---|---|---|
| CN117604455A (en) * | 2023-12-06 | 2024-02-27 | 河海大学 | Hydrothermal preparation method of magnesium alloy surface magnesium aluminum layered double metal hydroxide film based on self-supply of metal elements |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090221058A1 (en) * | 2008-02-29 | 2009-09-03 | Chung Yuan Christian University | Potentiometric biosensor for detection of lactate in food and forming method thereof |
| CN103864156A (en) * | 2012-12-13 | 2014-06-18 | 北京市太阳能研究所集团有限公司 | Nickel oxide composite film preparation method and film prepared by preparation method |
| CN111188058A (en) * | 2020-02-10 | 2020-05-22 | 桂林电子科技大学 | System for producing hydrogen by full-film silicon semiconductor double-electrode unbiased photoelectrocatalysis full-decomposition of water and application thereof |
| CN112176338A (en) * | 2020-09-04 | 2021-01-05 | 重庆大学 | Preparation method of ZnAL-LDHs film with amino acid ion intercalation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3214043A4 (en) * | 2014-10-28 | 2018-05-02 | NGK Insulators, Ltd. | Method for forming layered double hydroxide dense membrane |
-
2021
- 2021-09-24 CN CN202111120035.5A patent/CN113846289A/en active Pending
- 2021-11-08 WO PCT/CN2021/129240 patent/WO2023045042A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090221058A1 (en) * | 2008-02-29 | 2009-09-03 | Chung Yuan Christian University | Potentiometric biosensor for detection of lactate in food and forming method thereof |
| CN103864156A (en) * | 2012-12-13 | 2014-06-18 | 北京市太阳能研究所集团有限公司 | Nickel oxide composite film preparation method and film prepared by preparation method |
| CN111188058A (en) * | 2020-02-10 | 2020-05-22 | 桂林电子科技大学 | System for producing hydrogen by full-film silicon semiconductor double-electrode unbiased photoelectrocatalysis full-decomposition of water and application thereof |
| CN112176338A (en) * | 2020-09-04 | 2021-01-05 | 重庆大学 | Preparation method of ZnAL-LDHs film with amino acid ion intercalation |
Non-Patent Citations (1)
| Title |
|---|
| JAEWAN SHIN ET AL: "Zn-Al Layered Double Hydroxide Thin Film Fabricated by the Sputtering Method and Aqueous Solution Treatment", 《COATINGS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117604455A (en) * | 2023-12-06 | 2024-02-27 | 河海大学 | Hydrothermal preparation method of magnesium alloy surface magnesium aluminum layered double metal hydroxide film based on self-supply of metal elements |
| CN117604455B (en) * | 2023-12-06 | 2024-08-23 | 河海大学 | Hydrothermal preparation method of magnesium alloy surface magnesium aluminum layered double metal hydroxide film based on self-supply of metal elements |
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