CN114196930A - Thin film catalyst material with nanosheet array structure and preparation method thereof - Google Patents

Thin film catalyst material with nanosheet array structure and preparation method thereof Download PDF

Info

Publication number
CN114196930A
CN114196930A CN202111539315.XA CN202111539315A CN114196930A CN 114196930 A CN114196930 A CN 114196930A CN 202111539315 A CN202111539315 A CN 202111539315A CN 114196930 A CN114196930 A CN 114196930A
Authority
CN
China
Prior art keywords
thin film
array structure
catalyst material
film catalyst
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111539315.XA
Other languages
Chinese (zh)
Inventor
张博
刘青青
鲁直
胡青卓
周锦涛
甘雨
吴东燕
鲁迪
黄圆圆
许苏
陆禹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei University of Technology
Original Assignee
Hefei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hefei University of Technology filed Critical Hefei University of Technology
Priority to CN202111539315.XA priority Critical patent/CN114196930A/en
Publication of CN114196930A publication Critical patent/CN114196930A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a thin film catalyst material with a nano-sheet array structure and a preparation method thereof. The material obtained by the invention not only has good alcohol catalysis property, but also has the characteristics of large specific surface area and favorable carrier transmission, so that the material can be used as a carrier material to realize the application in various fields, such as the fields of photoelectric detectors, organic matter degradation, supported catalysts and the like.

Description

Thin film catalyst material with nanosheet array structure and preparation method thereof
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a thin film catalyst material with a nanosheet array structure and a preparation method thereof.
Background
The magnetic field is applied to the preparation process of the nano-structure material, so that the controlled growth of the nano-material arrangement structure is realized, and the method belongs to the field of electromagnetic process processing (EPM) research of materials.
The electromagnetic process processing of the material originates from magnetohydrodynamics, which is proposed first by Alfven in the fortieth past century, the initial magnetohydrodynamics is the science for researching the mutual relation between an electromagnetic field and a conductive fluid, the material is initially applied to the field of metallurgy in the production of the material, the field science is continuously developed and developed along with the widening of the application field and the popularization of the acting material, and more novel materials are developed successively.
Currently, researchers have found that there are four effects of magnetic fields on materials: the magnetic force action, the Lorentz force action, the magnetocaloric force action and the magnetic orientation action are mainly used for controlling the diffusion process among metal elements and the growth direction of the material in the preparation of the nano-structure material by the dealloying method, so that the final nano-structure of the dealloying sample is influenced. The invention takes the method as the starting point to research the preparation technology of the thin film catalyst material with the nano-sheet array structure under the action of the magnetic field.
Disclosure of Invention
The invention provides a preparation method of a thin film catalyst material with a nanosheet array structure, and aims to enable the material to have a nanosheet array structure.
The invention adopts the following technical scheme for realizing the purpose:
a preparation method of a thin film catalyst material with a nanosheet array structure is characterized by comprising the following steps:
step 1, preparing AlCuNi alloy film
Taking a CuAl target and a Ni target, and obtaining an AlCuNi alloy film on a substrate by adopting a co-sputtering method on a magnetron sputtering coating instrument;
step 2, preparing the thin film catalyst material with the nanosheet array structure
Soaking the AlCuNi alloy film and the substrate in a glassware filled with dealloying corrosive liquid, then placing the glassware in a magnetic field formed by a permanent magnet, and naturally dealloying at room temperature to obtain the film catalyst material with the nano-sheet array structure.
Preferably, the AlCuNi alloy film comprises Al in atomic percentage80Cu8Ni12。
Preferably, the magnetic field of the permanent magnet is 0.3-0.4T.
Preferably, the selected dealloying corrosion solution is 0.1mol/L KOH solution.
Preferably, the substrate is a silver foil with a purity of 99.9%.
The thin film catalyst material with the nanosheet array structure prepared by the invention has alcohol electrocatalytic performance.
Compared with the prior art, the invention has the beneficial effects that:
1. the thin film catalyst material with the nano-sheet array structure is prepared by adopting a one-step dealloying method, not only has good alcohol catalytic property, but also has the characteristics of large specific surface area and benefit for carrier transmission, so that the thin film catalyst material can be used as a carrier material, and can be used in various fields such as the fields of photoelectric detectors, degradation of organic matters, supported catalysts and the like by purposefully loading other functional materials.
2. The preparation method of the invention does not use noble metal materials, and the cost of raw materials is lower.
3. The invention introduces magnetic field energy, namely, by directionally applying a magnetic field and utilizing the orientation effect of the magnetic field on the magnetic components in the alloy film, the diffusion rearrangement process of the alloy film in the dealloying process is influenced, and the nano-sheet array structure is obtained.
4. The preparation method is simple, easy to operate, low in cost and environment-friendly, does not need special equipment in the whole preparation process, and is easy for large-scale industrial production.
Drawings
FIG. 1 is a schematic view showing the placement of a magnetic field and an alloy thin film in the process of dealloying in example 1.
Fig. 2 is an XPS diagram of the nanosheet array structured thin film catalyst prepared in example 1, corresponding to (a) Al 2p, (b) Cu 2p, (c) Ni 2p, (d) O1 s.
FIG. 3 is an SEM image of a sample obtained by the alloy film of example 1 under the condition of no loading and no loading of magnetic field during the dealloying process, wherein (a) and (b) are respectively the surface topography and the profile topography of the sample obtained under the condition of no loading of magnetic field, and (c) and (d) are respectively the surface topography and the profile topography of the sample obtained under the condition of loading of magnetic field.
FIG. 4 is an alcohol electrocatalytic characteristic curve of the thin film catalyst with a nanosheet array structure prepared in example 1, wherein (a) is a C-V curve and (b) is an i-t curve.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. The following disclosure is merely exemplary and illustrative of the inventive concept, and those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
The model of the magnetron sputtering coating equipment of the following embodiment is as follows: JS-500CK, Hefeijoshuo vacuum technology Co., Ltd, China.
The chemical states of elements of the thin film catalyst material with the nanosheet array structure obtained in the following example are detected by an X-ray photoelectron spectrometer (XPS), and the types of the used equipment are as follows: ESCALAB250Xi, Thermo, usa.
The surface and the section morphology of the thin film catalyst with the nano-sheet array structure obtained in the following embodiment are detected by a field emission Scanning Electron Microscope (SEM), and the used equipment model is as follows: gemini500, germany.
The alcohol electrocatalysis performance test of the thin film catalyst with the nanosheet array structure obtained in the following embodiment adopts an electrochemical workstation for detection, and the types of the used equipment are as follows: CHI760E, shanghai chenhua.
Example 1
Alloy raw material Cu used in this example33Al67The purity of the alloy target and the Ni target is more than or equal to 99.99 percent.
This example prepares a thin film catalyst with a nanosheet array structure as follows:
step 1, preparing AlCuNi alloy film
Cu with specification of phi 50x 3mm33Al67The target and the Ni target are put on a target head of a vacuum magnetron sputtering coating machine, and the vacuum degree reaches 3 multiplied by 10-4Introducing argon protective gas after Pa, simultaneously adjusting a flashboard of a molecular pump to maintain the pressure of a chamber at 0.5Pa, opening control power supplies of the two targets to pre-sputter for 5 minutes, controlling the component proportion of the two target material sputtering materials by adjusting the current and the voltage of the control power supplies, moving a baffle below a turntable to normally sputter the target materials on a silver foil after the glow of the target materials is stabilized, and finally obtaining Al80Cu8Ni12And (3) an alloy film.
Step 2, preparing the thin film catalyst material with the nanosheet array structure
In a glassware, dissolving KOH particles in deionized water to prepare a KOH solution with the concentration of 0.1 mol/L;
mixing Al80Cu8Ni12The alloy film and the substrate are soaked in a KOH solution, then the glassware soaked with the alloy film is placed in a magnetic field formed by a permanent magnet, the magnetic field intensity is 0.3-0.4T, the surface of the alloy film is close to the permanent magnet, the permanent magnet is naturally dealloyed at room temperature for 48h and then taken out, and distilled water and alcohol are alternately cleaned for a plurality of times, so that the thin film catalyst material with the nanosheet array structure is obtained.
Step 3, testing the electro-catalysis performance of the thin film catalyst with the nanosheet array structure on ethanol
Respectively preparing 0.5mol/L KOH and 0.5mol/L KOH +1mol/L ethanol electrolyte;
the C-V curve was tested in an electrolyte of 0.5mol/L KOH and 0.5mol/L KOH +1.0mol/L ethanol, and the i-t curve was tested in an electrolyte of 0.5mol/L KOH +1.0mol/L ethanol. Wherein, the film is used as a working electrode, the platinum sheet electrode is used as a counter electrode, and the reference electrode is a mercury oxide electrode.
FIG. 1 is a schematic diagram illustrating the placement of the magnetic field and the alloy thin film during the dealloying process of this embodiment. As shown in the figure, a glass vessel filled with KOH corrosive liquid is placed above the permanent magnet, and Al80Cu8Ni12The alloy film and the substrate are soaked in KOH solution, the substrate is arranged on the upper surface, and the alloy film layer is arranged downwards and close to the permanent magnet.
Fig. 2 shows XPS spectra of the thin film catalyst with nanosheet array structure prepared in this example, wherein the XPS spectra are (a) Al 2p, (b) Cu 2p, (c) Ni 2p, and (d) O1 s. The Al 2p energy spectrum consists of two peaks, corresponding to Al and Al2O3The two peaks on the left and right are the 3p orbitals of Cu and Ni. The Cu 2p energy spectrum consists of three peaks which are respectively Cu 2p3/2And Cu 2p1/2Corresponding to CuO, Cu (OH)2And Cu2And O. The Ni 2p energy spectrum is composed of two peaks, namely Ni 2p3/2And Ni 2p1/2Corresponding to NiO and Ni. O1 s energy spectrum corresponding to OH-。
FIG. 3 is an SEM image of the sample obtained by the alloy thin film of the present embodiment without loading and loading magnetic field during the dealloying process. Wherein, the surface and the section appearance of the dealloying sample are shown in a figure a and a figure b when the magnetic field is not loaded, and the surface and the section appearance of the dealloying sample are shown in a figure c and a figure d when the magnetic field is loaded. The comparison shows that the nano-sheet structure does not appear when the magnetic field is not loaded, and the nano-sheet array structure appears when the magnetic field is loaded, which indicates that the introduction of the magnetic field energy promotes the formation of the nano-sheet array structure.
Fig. 4 is an alcohol catalysis characteristic curve of the thin film catalyst with a nanosheet array structure prepared in this example. Graph a is a comparison of C-V with and without ethanol, and graph b is a graph of i-t tested in KOH solution with ethanol. The catalyst has better electro-catalytic performance to ethanol, and the catalytic performance of the catalyst is very stable within 6000 seconds.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A preparation method of a thin film catalyst material with a nanosheet array structure is characterized by comprising the following steps:
step 1, preparing AlCuNi alloy film
Taking a CuAl target and a Ni target, and obtaining an AlCuNi alloy film on a substrate by adopting a co-sputtering method on a magnetron sputtering coating instrument;
step 2, preparing the thin film catalyst material with the nanosheet array structure
Soaking the AlCuNi alloy film and the substrate in a glassware filled with dealloying corrosive liquid, then placing the glassware in a magnetic field formed by a permanent magnet, and naturally dealloying at room temperature to obtain the film catalyst material with the nano-sheet array structure.
2. The method of claim 1, wherein: the AlCuNi alloy film comprises Al according to atomic percentage80Cu8Ni12。
3. The method of claim 1, wherein: the magnetic field of the permanent magnet is 0.3-0.4T.
4. The method of claim 1, wherein: the selected dealloying corrosive liquid is 0.1mol/L KOH solution.
5. The method of claim 1, wherein: the substrate is a silver foil with the purity of 99.9 percent or a silicon wafer with a polished single surface.
6. A thin film catalyst material with a nanosheet array structure prepared by the preparation method of any one of claims 1 to 5.
7. The thin film catalyst material of claim 6, wherein: the thin film catalyst material has alcohol electrocatalytic properties.
CN202111539315.XA 2021-12-15 2021-12-15 Thin film catalyst material with nanosheet array structure and preparation method thereof Pending CN114196930A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111539315.XA CN114196930A (en) 2021-12-15 2021-12-15 Thin film catalyst material with nanosheet array structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111539315.XA CN114196930A (en) 2021-12-15 2021-12-15 Thin film catalyst material with nanosheet array structure and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114196930A true CN114196930A (en) 2022-03-18

Family

ID=80654322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111539315.XA Pending CN114196930A (en) 2021-12-15 2021-12-15 Thin film catalyst material with nanosheet array structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114196930A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191400A (en) * 2011-05-06 2011-09-21 上海大学 Dealloying preparation method of nanoporous metal under static magnetic field
CN103866256A (en) * 2014-03-20 2014-06-18 常州大学 Preparation method of metal oxide-porous nano films (MO-PNFs)
US20160010228A1 (en) * 2014-07-11 2016-01-14 University Of Delaware Electrocatalyst for hydrogen evolution and oxidation reactions
CN107398554A (en) * 2017-06-23 2017-11-28 中国工程物理研究院材料研究所 A kind of method that de- alloy of chemistry prepares the micro-nano laminated structures of Cu
CN108385069A (en) * 2018-03-30 2018-08-10 西安理工大学 A kind of preparation method of hyperfine nano multihole copper film
KR20180131236A (en) * 2017-05-31 2018-12-10 한국전력공사 Manufacturing method of porous nanostructure electrode, porous nanostructure electrode theryby and ruel cell comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191400A (en) * 2011-05-06 2011-09-21 上海大学 Dealloying preparation method of nanoporous metal under static magnetic field
CN103866256A (en) * 2014-03-20 2014-06-18 常州大学 Preparation method of metal oxide-porous nano films (MO-PNFs)
US20160010228A1 (en) * 2014-07-11 2016-01-14 University Of Delaware Electrocatalyst for hydrogen evolution and oxidation reactions
KR20180131236A (en) * 2017-05-31 2018-12-10 한국전력공사 Manufacturing method of porous nanostructure electrode, porous nanostructure electrode theryby and ruel cell comprising the same
CN107398554A (en) * 2017-06-23 2017-11-28 中国工程物理研究院材料研究所 A kind of method that de- alloy of chemistry prepares the micro-nano laminated structures of Cu
CN108385069A (en) * 2018-03-30 2018-08-10 西安理工大学 A kind of preparation method of hyperfine nano multihole copper film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAIXIA ZHANG.ET AL.: "《The effect of an external magnetic field on the dealloying process of the Ni-Al alloy in alkaline solution》", 《PHYS. CHEM. CHEM. PHYS》, vol. 19, pages 18167 *
王子玉等: "《微掺杂Ni对纳米多孔铜微观结构和电化学性能的影响》", 《功能材料》, vol. 47, no. 12, pages 1 - 3 *

Similar Documents

Publication Publication Date Title
CN110284102A (en) A kind of metal carbides crystal composite coating and preparation method thereof
JP2016540118A (en) Electrochemical cell with graphene-covered electrode
CN109943857B (en) Silicon-based photoelectrode, and preparation method and application thereof
CN210628419U (en) Metal bipolar plate coating of fuel cell
Nie et al. Co–Ni nanowires supported on porous alumina as an electrocatalyst for the hydrogen evolution reaction
CN111841589B (en) Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof
Hrbek et al. Sputter-etching treatment of proton-exchange membranes: Completely dry thin-film approach to low-loading catalyst-coated membranes for water electrolysis
CN103526227A (en) Method for preparing composite electrode
CN114481048A (en) High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexistent coating and preparation method and application thereof
CN114464818A (en) Low-cost surface treatment method for improving surface performance of titanium and titanium alloy for proton exchange membrane fuel cell polar plate
CN113718282A (en) Preparation method of hydrogen evolution platinum coating electrode material for hydrogen production by water electrolysis
CN114196930A (en) Thin film catalyst material with nanosheet array structure and preparation method thereof
CN117144296A (en) Preparation method of hydrogen fuel cell polar plate coating
CN112820890A (en) Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate
CN114411016B (en) Self-supporting nanoporous Ni 4 Preparation method and application of Mo/Ni alloy material
Samsudin et al. Deposition and characterization of RF-sputtered-Ta2O5 thin films for O2 reduction reaction in polymer electrolyte membrane fuel cells (PEMFC)
KR20140067193A (en) Method of manufacturing porous composite thin film and the porous composite thin film for electrode
CN107293605A (en) Back electrode of solar cell and solar cell and preparation method thereof
CN1283015C (en) Multi-layer film electrode for nickle-hydrogen cell and preparation method thereof
CN216107248U (en) Photoelectrode and Pt-based nano alloy catalyst
CN109837516A (en) A kind of magnetron sputtering preparation ZnFe2O4/Fe2O3The method of 3-D heterojunction nano material
CN115233170B (en) Ultrathin metal oxide-based nanomaterial with high catalytic performance as well as preparation method and application thereof
CN110295355A (en) A kind of preparation method of wolframic acid stannous film that realizing continuous photocatalytic water
CN112725750B (en) Method for preparing BVO epitaxial single crystal film by magnetron sputtering technology
CN111293324B (en) Anti-oxidation gas diffusion layer of fuel cell and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination