CN113189264B - Method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst - Google Patents

Method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst Download PDF

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CN113189264B
CN113189264B CN202110477593.0A CN202110477593A CN113189264B CN 113189264 B CN113189264 B CN 113189264B CN 202110477593 A CN202110477593 A CN 202110477593A CN 113189264 B CN113189264 B CN 113189264B
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sample library
electrode
alloy
flux
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CN113189264A (en
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刘烜志
邹鹏
王军强
霍军涛
许巍
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Ningbo Institute of Material Technology and Engineering of CAS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
    • 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
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    • 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
    • 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
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    • 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
    • C23C14/3464—Sputtering using more than one target
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    • 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
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst. The method comprises the following steps: preparing a high-flux film sample library by adopting PVD co-sputtering, wherein the high-flux film sample library consists of a plurality of multi-principal-element electrolytic water catalysts with different alloy components; and adopting a three-electrode system, taking the high-flux film sample library as a working electrode, electrifying the three-electrode system to perform electrolytic water reaction, recording bubble information on the surface of the high-flux film sample library in real time, and judging and screening HER catalytic activity of each area on the surface of the high-flux film sample library at least according to the volume of bubbles. The invention provides a method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst, which mainly comprises two parts of preparation of a high-throughput film sample library and parallel high-throughput screening; the method can rapidly screen out the multi-component alloy with the highest catalytic performance, and further determine the multi-principal-element electrolytic water catalyst with excellent HER catalytic activity.

Description

Method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst
Technical Field
The invention belongs to the technical field of water electrolysis catalysts, and particularly relates to a method for high-throughput parallel screening of a multi-principal-element water electrolysis catalyst.
Background
Electrochemical water splitting has been widely used as a means of secondary energy storage for chemical fuels. Because it can effectively produce high-purity H in large scale 2 Without negative environmental impact, it has become one of the most widely studied energy research fields. Therefore, it is important to develop an electrolyzed water catalyst having high catalytic activity and good durability.
Over the last decades, catalysts based on non-precious transition metals, such as alloys, carbides, nitrides, phosphides, borides, have been developed. However, the development of multi-component catalysts at the present stage is based on sequential trial and error methods, which are both time consuming and laborious. Particularly how the amount of the alloy increases sharply with the amount of the alloy components.
At present, the development of the multi-principal element water electrolysis catalyst is mainly a trial-and-error method, taking the water electrolysis catalyst of an alloy strip as an example, the method mainly comprises the following four main steps: 1) Selecting required metal raw materials, and proportioning the raw materials by an electronic scale according to the atomic percentage; 2) Putting the proportioned materials into a high-temperature smelting furnace, and preparing raw materials into a multi-element alloy spindle; 3) Putting the smelted spindle into a high-speed roller flail machine, and preparing the material into strips; 4) The strips were prepared as working electrodes and tested for electrolytic water catalytic performance. Only one sample of the target component can be prepared in the whole process, and the electrolytic water catalytic performance of one sample is evaluated after the test. For a plurality of samples with different components, the process needs to be repeated for a plurality of times, a large amount of manpower and financial resources are needed, the cost is high, and the problems of long test period and low test efficiency exist.
Disclosure of Invention
The invention mainly aims to provide a method for high-throughput parallel screening of multi-principal-element electrolyzed water catalysts so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for high-throughput parallel screening of multi-principal-element electrolyzed water catalyst, which comprises the following steps:
preparing a high-flux film sample library by PVD co-sputtering, wherein the high-flux film sample library consists of a plurality of multi-principal-element electrolytic water catalysts with different alloy components;
and adopting a three-electrode system, taking the high-flux film sample library as a working electrode, electrifying the three-electrode system to carry out electrolytic water reaction, recording bubble information on the surface of the high-flux film sample library in real time, and judging and screening HER catalytic activity of each area on the surface of the high-flux film sample library at least according to the volume of bubbles.
The embodiment of the invention also provides the multi-principal-element electrolyzed water catalyst obtained by screening by the method.
The embodiment of the invention also provides the application of the method in the field of water electrolysis.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for high-throughput parallel screening of multi-principal element electrolytic water catalysts, which mainly comprises two parts, namely preparation of a high-throughput film sample library and parallel high-throughput screening; the method can rapidly screen out the multi-component alloy with the highest catalytic performance, and further determine the multi-principal-element electrolytic water catalyst with excellent HER catalytic activity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of an apparatus for PVD co-sputter deposition of a high throughput thin film sample library in an exemplary embodiment of the invention;
FIG. 2 is a schematic diagram of an apparatus for parallel high throughput bubble screening in an exemplary embodiment of the invention;
FIGS. 3 a-3 b are schematic diagrams of the high-throughput thin film sample library prepared in example 1 of the present invention and ternary composition diagrams of the high-throughput thin film sample library;
FIG. 4 is a statistical chart of bubble volumes during parallel screening of high-throughput thin film sample libraries in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solutions of the present invention, which will be clearly and completely described below. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for high-throughput parallel screening of multi-principal-element electrolyzed water catalysts, which comprises:
preparing a high-flux film sample library by adopting PVD co-sputtering, wherein the high-flux film sample library consists of a plurality of multi-principal-element electrolytic water catalysts with different alloy components;
and adopting a three-electrode system, taking the high-flux film sample library as a working electrode, electrifying the three-electrode system to carry out electrolytic water reaction, recording bubble information on the surface of the high-flux film sample library in real time, and judging and screening HER catalytic activity of each area on the surface of the high-flux film sample library at least according to the volume of bubbles.
In some more specific embodiments, the method comprises:
providing a substrate and at least two targets capable of forming an alloy;
and depositing a plurality of multi-principal element electrolytic water catalysts with different alloy components on the surface of the substrate by adopting PVD co-sputtering so as to form the high-flux film sample library, wherein the multi-principal element electrolytic water catalysts with different alloy components are arranged in a gradient manner.
Further, the gradient arrangement is arranged according to component gradient, namely, the percentage of different elements. In the case of binary, the alloy composition can be varied continuously from 100% Ni-0% Co to 50% Ni-50% Co to 0% Ni-100%.
Further, the thickness of the high-flux film sample library is 50 nm-10 mu m.
Further, the base material includes any one of Cu, fe, ag, al, ti, ta, mo, W, and is not limited thereto. The main purpose of selecting good conductors is to ensure that the potentials at different parts are the same (to provide the same conditions and to exclude external influences), and the effects of semiconductors such as Si, ITO and the like and poor conduction are not good (because the voltage drop is obvious due to overlarge resistance, more electric energy is converted into heat energy, and the conditions of the whole gradient sample cannot be ensured to be consistent).
Furthermore, the inclination angle of a sputtering target used in the multi-target PVD co-sputtering process is adjusted to control the deposition to form a plurality of multi-principal element electrolyzed water catalysts with different alloy component contents.
Further, and/or, the PVD co-sputtering includes any one of magnetron sputtering, evaporation, and ink printing, and is not limited thereto.
In some more specific embodiments, the method comprises:
the high-flux film sample library is used as a working electrode, and the working electrode, the reference electrode, the counter electrode and the electrolyte form a three-electrode system;
electrifying the three-electrode system to carry out electrolytic water reaction, observing bubble information on the surface of the high-flux film sample library by using an optical microscope, recording and analyzing in real time, and judging the HER catalytic activity of each area on the surface of the high-flux film sample library according to the volume of bubbles, thereby screening out the multi-principal element electrolytic water catalyst with high HER catalytic activity in each area on the surface of the high-flux film sample library.
Further, the reference electrode includes any one of an Ag/AgCl electrode, a calomel electrode, a mercury-mercury oxide electrode, and a mercury-mercurous sulfate electrode, but is not limited thereto.
Further, the counter electrode includes any one of a Pt electrode, a graphite electrode, and a titanium electrode, and is not limited thereto.
Further, the Pt electrode includes any one of a platinum sheet electrode, a platinum mesh electrode, a platinum column electrode, and a platinum wire electrode, and is not limited thereto.
Further, the high-flux film sample library is inverted in the electrolyte. Wherein the sample film is inverted to ensure that bubbles are not desorbed and improve the hydrogen evolution activity precision.
Further, the optical microscope can be used for photographing and video recording for detecting the bubble information on the surface of the high-throughput thin film sample library. The optical microscope can be zoomed, and has the advantages of integration and detail. The camera can take pictures and record video to detect dynamic change. The process and volume of surface bubble generation can be characterized in situ. In some more specific embodiments, the multi-principal element electrolytic water catalyst is a multi-principal element alloy.
Further, the multi-principal element electrolytic water catalyst comprises any one of binary alloy, ternary alloy, quaternary alloy, quinary alloy, hexabasic alloy, heptabasic alloy and octabasic alloy, preferably ternary alloy, such as Ni-Co-Ti ternary alloy.
Further, the elements contained in the alloy include any one of Fe, co, ni, cu, ti, mo, W, mn, pt, pd, ir, ag, au, P, B, and C, but are not limited thereto.
In some more specific embodiments, the method for high throughput parallel screening of Ni-Co-Ti ternary alloys comprises:
1. preparation of Ni-Co-Ti ternary alloy high-flux film sample library (the schematic device of PVD Co-sputtering deposition high-flux film sample library is shown in figure 1):
synthesizing a high-flux thin film sample library by PVD Co-sputter deposition, wherein pure Ni, co and Ti metals are used in three sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the Cu sheet has extremely low resistivity, the potential of the whole thin film sample library in the electrochemical test process can be ensured to be the same, (if the resistivity of a substrate is large, such as Si, ITO or other substrates with low conductivity, the potential gradient is too large to determine the HER performance of the sample library) the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a chamber is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of Ni is 40-60W, the sputtering power of Co is 40-60W, the sputtering power of Ti is 70-90W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element;
2. parallel high-throughput screening (fig. 2 is a schematic diagram of an apparatus for parallel high-throughput bubble screening):
(1) Packaging the high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) Adopting a standard three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement process, the surface information of the whole high-throughput thin film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined by the volume of the hydrogen bubbles and the HER catalytic activity can be determined by the volume of the bubbles;
(7) And drawing a performance graph and finding out the components corresponding to the high-performance area.
In another aspect of the embodiments of the present invention, there is also provided a multi-principal element electrolyzed water catalyst obtained by the screening of the foregoing method.
Another aspect of an embodiment of the invention also provides the use of the aforementioned method in the field of electrolysis of water.
Another aspect of the embodiments of the present invention also provides a method for screening multiple principal element electrolyzed water catalysts in parallel, which includes:
taking a high-flux film sample library as a working electrode, and then forming the three-electrode system together with a reference electrode and a counter electrode, wherein the high-flux film sample library comprises a plurality of multi-principal-element electrolytic water catalysts with different alloy component contents;
electrifying the three-electrode system to carry out electrolytic water reaction, observing bubble information on the surface of the high-flux film sample library by using an optical microscope, recording and analyzing in real time, and judging the HER catalytic activity of each area on the surface of the high-flux film sample library according to the volume of bubbles, thereby screening out the multi-principal element electrolytic water catalyst with high HER catalytic activity in each area on the surface of the high-flux film sample library.
Further, the reference electrode includes an Ag/AgCl electrode, and is not limited thereto.
Further, the counter electrode includes a Pt electrode, and is not limited thereto.
Further, the high-flux film sample library is prepared by PVD co-sputtering.
Further, the multi-principal element electrolytic water catalyst is a multi-principal element alloy.
Further, the multi-principal element electrolytic water catalyst includes a ternary alloy, and is not limited thereto.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples below were obtained from conventional biochemicals unless otherwise specified.
Example 1
1. Preparing a Ni-Co-Ti ternary alloy high-throughput film sample library:
synthesizing a high-flux film sample library by PVD Co-sputtering deposition, wherein pure Ni, co and Ti are used in three sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of Ni is 40-60W, the sputtering power of Co is 40-60W, the sputtering power of Ti is 70-90W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element. High throughput of depositionThe chemical composition of the high throughput thin film sample library was measured using Energy Dispersive Spectroscopy (EDS) analysis and the compositional variation of the high throughput thin film sample library was: ni is 39-69 at.%, co is 22-50 at.%, and Ti is 5.5-20 at.%; the thickness of the high-flux film sample library is about 250nm, the contact between the high-flux film sample library and a base material is firm and the elements are uniformly distributed without segregation or precipitation through a transmission electron microscope, and then the high-flux film sample library is analyzed by using high-resolution micro-area X-ray diffraction (HRXRD), and the whole high-flux film sample library is of a single-phase FCC structure; fig. 3 a-3 b are chemical composition gradient coverage maps of the high-throughput thin film sample library prepared in this example, fig. 3a represents the sample library prepared in this example, where the numbers correspond to fig. 3b, fig. 3b is a ternary composition map, where each point corresponds to a specific composition, and the curve in fig. 3b represents the composition gradient coverage of a single sample library in fig. 3 a.
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) Adopting a standard three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement process, the surface information of the whole high-throughput thin film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined from the volume of the hydrogen bubbles and HER catalytic activity can be determined from the volume of the bubbles;
(7) Plotting a performance graphTo find out the corresponding components of the high performance region, FIG. 4 is a statistical chart of the bubble volume during parallel screening according to the embodiment of the present invention, as can be obtained from FIG. 4, where the contrast in FIG. 4 represents the volume of the generated bubbles, and the bright region is Ni, which is the region with high bubble generation (i.e. the region with good HER performance) 56.5 Co 35 Ti 8.5 HER performance is best in the region around at.%.
Example 2
1. Preparing a Fe-Cu-Mo ternary alloy high-throughput film sample library:
synthesizing a high-flux film sample library by PVD co-sputtering deposition, wherein pure Fe, cu and Mo metals are used in three sputtering targets, a Ti sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 45min, wherein the sputtering power of Fe is 20-80W, the sputtering power of Cu is 40-120W, the sputtering power of Mo is 40-120W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element. The chemical composition of the deposited high-throughput thin film sample library was measured using Energy Dispersive Spectroscopy (EDS) analysis, and the composition of the high-throughput thin film sample library varied over the range of: 50-80 at.% of Fe, 10-40 at.% of Cu and 5-25 at.% of Mo; the thickness of the high-flux thin film sample library is about 400nm, the contact between the high-flux thin film sample library and a substrate is firmly confirmed through a transmission electron microscope, elements are uniformly distributed, and segregation or precipitation is avoided, and then the phase structure of the whole high-flux thin film sample library is confirmed through analysis by high-resolution micro-area X-ray diffraction (HRXRD).
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) Adopting a standard three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement, the surface information of the whole high-throughput thin-film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined from the volume of the hydrogen bubbles and HER catalytic activity can be determined from the volume of the bubbles;
(7) Plotting the performance plots, comparative, fe 63-66 Cu 27-30 Mo 5-10 HER performance in the at.% region is better.
Example 3
1. Preparing a Ni-Co binary alloy high-flux film sample library:
synthesizing a high-flux film sample library by PVD Co-sputtering deposition, wherein pure Ni and Co metals are used in two sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of Ni is 30-70W, the sputtering power of Co is 30-70W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element. The chemical composition of the deposited high-throughput thin film sample library was measured using Energy Dispersive Spectroscopy (EDS) analysis, and the composition of the high-throughput thin film sample library varied over the range of: ni is 30-80 at.%, co is 20-70 at.%; the thickness of the high-flux film sample library is about 250nm, the contact between the high-flux film sample library and the substrate is firm, the element distribution is uniform, and the segregation or the precipitation does not exist, and then the high-flux film sample library is analyzed by using high-resolution micro-area X-ray diffraction (HRXRD), and the whole high-flux film sample library is of an FCC NiCo solid solution structure.
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) Adopting a standard three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement process, the surface information of the whole high-throughput thin film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined by the volume of the hydrogen bubbles and the HER catalytic activity can be determined by the volume of the bubbles;
(7) Drawing a performance graph, and comparing: ni 62-66 C o34-38 HER performance in the at.% region is better.
Example 4
1. Preparing a Ni-Co-Ti-Au quaternary alloy high-flux film sample library:
synthesizing a high-flux film sample library by PVD Co-sputtering deposition, wherein pure Ni, co, ti and Au are used in four sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of Ni is 40-80W, the sputtering power of Co is 40-80W, the sputtering power of Ti is 80-120W, and the sputtering power of Au is 30-60W; the compositional gradient of the sputtering alloy high flux thin film sample library is controlled by the tilt angle of the target elements. Chemical composition of deposited high throughput thin film sample libraryThe measurements were performed by Energy Dispersive Spectroscopy (EDS) analysis, and the high throughput thin film sample library varied in composition over the range of: 39-72 at.% of Ni, 20-52 at.% of Co, 5.5-20 at.% of Ti and 2-10at.% of Au; the thickness of the high-flux thin film sample library is about 200nm, the contact between the high-flux thin film sample library and a substrate is firmly confirmed through a transmission electron microscope, elements are uniformly distributed, and segregation or precipitation is avoided, and then the phase structure of the whole high-flux thin film sample library is confirmed through analysis by high-resolution micro-area X-ray diffraction (HRXRD).
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) A standard three-electrode system is adopted, a reference electrode is an Ag/AgCl electrode, and a counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement process, the surface information of the whole high-throughput thin film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined by the volume of the hydrogen bubbles and the HER catalytic activity can be determined by the volume of the bubbles;
(7) Plotting a performance graph, comparing, ni 55-58 Co 32-35 Ti 7-8 Au 2-3 HER performance in the at.% region is better.
Example 5
1. Preparing a Ni-Co-Ti-Fe-Ag quinary alloy high-throughput film sample library:
high flux thin films synthesized by PVD co-sputter depositionFilm sample library, pure Ti and Ag metals and NiCo and NiFe alloys are used in four sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow rate of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of NiFe is 50-100W, the sputtering power of NiCo is 40-60W, the sputtering power of Ti is 80-120W, the sputtering power of Ag is 30-80W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element. The chemical composition of the deposited high-throughput thin film sample library was measured using Energy Dispersive Spectroscopy (EDS) analysis, and the composition of the high-throughput thin film sample library varied over the range of: ni is 32-64at.%, co is 15-32at.%, ti is 8-30at.%, fe is 13-30at.%, and Ag is 2-10at.%; the thickness of the high-flux thin film sample library is about 500nm, the contact between the high-flux thin film sample library and a substrate is firmly confirmed through a transmission electron microscope, elements are uniformly distributed, and segregation or precipitation is avoided, and then the phase structure of the whole high-flux thin film sample library is confirmed through analysis by high-resolution micro-area X-ray diffraction (HRXRD).
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) Adopting a standard three-electrode system, wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement process, the surface information of the whole high-throughput thin film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined from the volume of the hydrogen bubbles and HER catalytic activity can be determined from the volume of the bubbles;
(7) Drawing a performance graph, and comparing: ni 41-43 Co 20-22 Ti 9-11 Fe 20-21 Ag 4-6 HER performance in the at.% region is better.
Example 6
1. Preparing a Fe-Co-B ternary alloy high-flux film sample library:
synthesizing a high-flux film sample library by PVD Co-sputtering deposition, wherein pure Fe and Co are used in two sputtering targets, a Cu sheet with the diameter of 50mm is used as a substrate, the composition gradient is controlled by adjusting the inclination angle of a sputtering gun, and the basic pressure in a cavity is lower than 10 -5 Pa, the working pressure is 0.5Pa, the flow of argon is 50 standard cubic centimeters per minute (SCCM), the deposition is carried out for 30min, wherein the sputtering power of Fe is 40-80W, the sputtering power of CoB is 50-70W, and the component gradient of the sputtering alloy high-flux film sample library is controlled by the inclination angle of a target element. The chemical composition of the deposited high-throughput thin film sample library was measured using Energy Dispersive Spectroscopy (EDS) analysis, and the composition of the high-throughput thin film sample library varied over the range of: fe is 65-90 at.%, co is 5-25 at.%, B is 3-20 at.%; the thickness of the high-flux thin film sample library is about 100nm, the contact between the high-flux thin film sample library and a substrate is firmly confirmed through a transmission electron microscope, elements are uniformly distributed, and segregation or precipitation is avoided, and then the phase structure of the whole high-flux thin film sample library is confirmed through analysis by high-resolution micro-area X-ray diffraction (HRXRD).
2. Parallel high-throughput screening:
(1) Packaging the prepared high-flux film sample library by using insulating glue, preparing an electrode by only exposing one surface of the high-flux film sample library, immersing the high-flux film sample library into an electrolyte, and enabling one surface of the high-flux film sample library to face downwards to serve as a working electrode to be detected;
(2) A standard three-electrode system is adopted, a reference electrode is an Ag/AgCl electrode, and a counter electrode is a Pt electrode;
(3) Applying a suitable constant voltage (or constant current) to the working electrode, and recording the change of the current (voltage) along with the time;
(4) During the electrochemical measurement, the surface information of the whole high-throughput thin-film sample library is captured in real time by an optical microscope. Recording the distribution of the bubbles on the lower surface in real time to generate information;
(5) Dividing the surface information of the captured high-flux film sample library, counting the bubble information of each area, and calculating the bubble volume of each area at the moment;
(6) Integrating the recorded bubble volume information, the hydrogen evolution current density can be determined by the volume of the hydrogen bubbles and the HER catalytic activity can be determined by the volume of the bubbles;
(7) Plotting the Performance plots, by comparison, fe 68-70 Co 23-25 B 5-10 HER performance in the at.% region is better.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and sections in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the invention.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or order in which certain actions are performed is not critical, so long as the present teachings remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (6)

1. The application of the method for high-flux parallel screening of the multi-principal element water electrolysis catalyst in the field of water electrolysis is characterized in that the method for high-flux parallel screening of the multi-principal element water electrolysis catalyst comprises the following steps:
providing a substrate and at least two targets capable of forming an alloy;
depositing a plurality of multi-principal element electrolytic water catalysts with different alloy components on the surface of the substrate by adopting PVD co-sputtering so as to form a high-flux film sample library, wherein the multi-principal element electrolytic water catalysts with different alloy components are arranged in a gradient manner; the thickness of the high-flux film sample library is 50nm to 10 mu m; the multi-principal element electrolytic water catalyst is a multi-principal element alloy, and elements contained in the multi-principal element alloy are selected from any one of Fe, co, ni, cu, ti, mo, W, mn, pt, pd, ir, ag, au, P, B and C; controlling to deposit and form a plurality of multi-principal element electrolyzed water catalysts with different alloy component contents by adjusting the inclination angle of a sputtering target used in the multi-target PVD co-sputtering process; the multi-principal element electrolytic water catalyst is selected from any one of binary alloy, ternary alloy, quaternary alloy, quinary alloy, hexahydric alloy, heptatomic alloy and octatomic alloy;
and the high-flux film sample library is used as a working electrode, and forms a three-electrode system together with a reference electrode, a counter electrode and electrolyte; electrifying the three-electrode system to carry out electrolytic water reaction, observing bubble information on the surface of the high-flux film sample library by using an optical microscope, recording and analyzing in real time, and judging the HER catalytic activity of each area on the surface of the high-flux film sample library according to the volume of bubbles so as to screen out the multi-principal element electrolytic water catalyst with high HER catalytic activity in each area on the surface of the high-flux film sample library; wherein the high-flux thin film sample library is inverted in the electrolyte.
2. Use according to claim 1, characterized in that: the substrate material is selected from any one of Cu, fe, ag, al, ti, ta, mo and W.
3. Use according to claim 1, characterized in that: the reference electrode is selected from any one of an Ag/AgCl electrode, a calomel electrode, a mercury-mercury oxide electrode and a mercury-mercurous sulfate electrode.
4. Use according to claim 1, characterized in that: the counter electrode is selected from any one of a Pt electrode, a graphite electrode and a titanium electrode; the Pt electrode is selected from any one of a platinum sheet electrode, a platinum mesh electrode, a platinum column electrode and a platinum wire electrode.
5. Use according to claim 1, characterized in that: the optical microscope is capable of taking pictures and video for detecting bubble information on the surface of the high-throughput thin film sample library.
6. Use according to claim 1, characterized in that: the multi-principal element water electrolysis catalyst is a ternary alloy.
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