CN114990613B - Amorphous bismuth oxygen selenium film composite electrode and preparation method and application thereof - Google Patents
Amorphous bismuth oxygen selenium film composite electrode and preparation method and application thereof Download PDFInfo
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- SYYDNLBOFQOSGT-UHFFFAOYSA-N [Bi]=O.[Se] Chemical compound [Bi]=O.[Se] SYYDNLBOFQOSGT-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 230000008021 deposition Effects 0.000 claims abstract description 19
- 238000005498 polishing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 62
- 239000013077 target material Substances 0.000 claims description 40
- 238000004544 sputter deposition Methods 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000843 powder Substances 0.000 abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 229910052799 carbon Inorganic materials 0.000 description 31
- 239000011521 glass Substances 0.000 description 31
- 230000003197 catalytic effect Effects 0.000 description 13
- VQNPRYUMHLOITA-UHFFFAOYSA-N [Se]O Chemical compound [Se]O VQNPRYUMHLOITA-UHFFFAOYSA-N 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses an amorphous bismuth oxygen selenium film composite electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: fully polishing the glassy carbon substrate by using alumina polishing powder, cleaning by using ultrasonic waves, and drying by using inert gas; the bismuth oxygen selenium film composite electrode is fixed on a sample stage of a pulse laser deposition system, bismuth oxygen selenium is used as a target, under the conditions of background vacuum with certain pressure and constant laser energy density, the bismuth oxygen selenium film composite electrode is prepared by pre-cauterizing, then removing a baffle plate for deposition and taking out a sample under the nitrogen atmosphere. The amorphous bismuth oxygen selenium film composite electrode is applied to an electrocatalytic moisture analysis oxygen reaction system, and can effectively catalyze and promote the electrolytic water oxygen analysis reaction. The invention shows that the amorphous structure engineering can be an effective and general strategy for designing the next generation of electrolytic water oxygen evolution reaction to apply high-performance catalysts.
Description
Technical Field
The invention relates to the technical field of composite electrode preparation, in particular to an amorphous bismuth oxygen selenium film composite electrode and a preparation method and application thereof.
Background
In the current society, the development of new clean energy is not easy due to the excessive exploitation of fossil energy and the increasingly worsened ecological environment. Electrochemical reactions are a simple method of efficiently providing and storing electrical energy through chemical bonds, which can be stored by electrochemically decomposing water to form hydrogen and oxygen. The potential of the electrolytic water is huge, the energy storage of the electrolytic water is also an important development trend, and the purity of the gas produced by the electrolytic water is almost 100%, and the electrolytic water is nontoxic and pollution-free. However, even with the most advanced catalysts, oxygen electrocatalysis severely limiting the energy efficiency and rate capability of electrochemical energy devices due to the large overpotential required to drive the reaction. Promoting the oxygen half-reaction with highly active, cost-effective catalysts is key to achieving widespread distribution and utilization of renewable energy sources by these devices.
Electrocatalyst IrO 2 And RuO (Ruo) 2 Are considered to be the catalysts with the strongest catalytic activity for Oxygen Evolution Reaction (OER), but the two catalysts have poor stability in the reaction process and high price, and cannot be applied to commercial and industrial production on a large scale. It has been shown that in recent years, highly symmetrical phase selenium oxide has proven to be a highly active and stable and low cost electrocatalyst that promotes OER in alkaline solutions, compared to expensive and scarce noble metal catalysts.
The bismuth oxygen selenium film has little research in the OER catalytic performance field, but the amorphous bismuth oxygen selenium film covered glass carbon sheet has better catalytic activity and stability in alkaline solution, and can effectively catalyze and promote the OER reaction.
Disclosure of Invention
Currently, bismuth oxygen selenium films are used as OER catalysts, and when oxygen evolution reactions occur, the catalyst surface can generate large amounts of oxygen that cause it to corrode, thereby causing serious consequences of catalyst decomposition. Meanwhile, the introduction of organic components such as adhesive can cover part of active sites on the surface of the catalyst, so that the catalyst is partially deactivated, and the catalytic effect and the utilization rate of the catalyst are reduced.
The invention aims to provide an amorphous bismuth oxygen selenium film composite electrode, a preparation method and application thereof, which can solve the problems that the bismuth oxygen selenium film is not easy to directly participate in electrocatalytic reaction, is easy to be corroded and shed in the reaction process, has few active sites, and has lower catalytic activity.
In order to achieve the above purpose, the invention adopts the following technical scheme.
The preparation method of the amorphous bismuth oxygen selenium film composite electrode comprises the following steps:
(1) Preparation of bismuth oxygen selenium target material
Weighing bismuth oxide and bismuth selenide according to a proportion, mixing, grinding and sintering to prepare a bismuth oxygen selenium target material;
(2) Substrate pretreatment
Polishing and ultrasonic cleaning are sequentially carried out on the conductive substrate glassy carbon, and then inert gas is used for drying for standby;
(3) Preparation of composite electrode
Placing the bismuth oxygen selenium target material prepared in the step (1) and the substrate prepared in the step (2) into a pulse laser deposition system, carrying out pre-sputtering on the bismuth oxygen selenium target material under the conditions of a vacuum environment and constant laser energy density after vacuumizing, carrying out laser firing on the bismuth oxygen selenium target material after the pre-sputtering is finished, depositing the bismuth oxygen selenium target material on the substrate, and taking out the bismuth oxygen selenium film under the nitrogen atmosphere to prepare the amorphous bismuth oxygen selenium film composite electrode.
The beneficial effects of adopting above-mentioned scheme are: firstly, preparing a bismuth oxygen selenium target material, and sintering the bismuth oxygen selenium target material into a columnar body, which can be suitable for placing the target material in a pulse laser deposition system; the polishing powder is used for fully polishing the glass carbon sheet to make the surface of the glass carbon sheet smooth and smooth, so that the bismuth oxygen selenium film can be covered conveniently, the prepared bismuth oxygen selenium amorphous film is conductive, and when the bismuth oxygen selenium amorphous film is used for catalyzing OER reaction, the bismuth oxygen selenium amorphous film needs to be conducted with a stainless steel electrode, so that the glass carbon sheet with better conductivity is needed to be used as a substrate. The bismuth oxygen selenium target material is subjected to pre-sputtering treatment, impurities on the surface of the target material can be removed, deposition is carried out at room temperature, the grown film is amorphous, the film is grown through a pulse laser sputtering deposition system, plasma is generated when laser is applied to the target material, and the plasma is attached to a substrate SrTiO 3 And forming a film on the substrate to prepare the amorphous bismuth oxygen selenium film composite electrode.
Further, in the step (1), the molar ratio of bismuth, oxygen and selenium atoms in the bismuth-oxygen-selenium target material is 2:2:1.
The beneficial effects of adopting above-mentioned scheme are: the molar ratio of bismuth, oxygen and selenium atoms in the bismuth-oxygen-selenium target is 2:2:1, so as to ensure the stoichiometric ratio of the target.
Further, in the step (1), the sintering temperature is 600-680 ℃ and the sintering time is 10-14h. Preferably the sintering temperature is 680 c and the sintering time is 12h.
The beneficial effects of adopting above-mentioned scheme are: the sintering time is longer, the sintering temperature is higher, bismuth oxide and bismuth selenide powder can be fully reacted, the bismuth oxygen selenium target is generated, and the target can be repeatedly used.
Further, the polishing and ultrasonic cleaning process in the step (2) comprises the following steps: firstly, the surface and the periphery of a glass carbon sheet are sufficiently polished by alumina polishing powder with the diameter of 20-200 nm. Then sequentially using acetone, absolute ethyl alcohol and deionized water to ultrasonically clean for 10-20min. Preferably, the diameter of the alumina polishing powder is 50nm, and the ultrasonic cleaning time is 15min.
The beneficial effects of adopting above-mentioned scheme are: the alumina polishing powder is sufficiently polished to enable the surface of the glass carbon sheet to be sufficiently smooth, so that the subsequent covering of the bismuth oxygen selenium film is facilitated, and the glass carbon sheet can be reused. The acetone can clean organic impurities on the glass carbon sheet, the absolute ethyl alcohol cleans the residual acetone on the glass carbon sheet, and the deionized water cleans the residual ethyl alcohol and other inorganic matters on the glass carbon sheet.
Further, the pressure in the deposition system after the vacuum pumping in the step (3) is 1.9X10 -4 -2.0×10 -4 Pa. Preferably the vacuum pressure is 1.9X10 -4 Pa。
The beneficial effects of adopting above-mentioned scheme are: the vacuum degree is low enough to ensure that impurities in the vacuum cavity are relatively less, and the interference of the impurities in the cavity on the growth of the film is eliminated as much as possible.
Further, the pre-sputtering time in the step (3) is 5-10min, and the laser sputtering time is 28-32min. Preferably, the pre-sputtering time is 5min and the laser sputtering time is 30min.
The beneficial effects of adopting above-mentioned scheme are: the impurities on the surface of the target material are removed by pre-sputtering, the impurities on the surface of the target material cannot be interfered when the film is deposited, and the thickness of the film can be adjusted by the laser sputtering time, so that the film can maintain the thickness under the optimal catalytic activity.
Further, the distance between the conductive substrate and the bismuth oxygen selenium target in the step (3) is 50-60mm, and the oxygen pressure in the growth process is 1-30Pa; the distance between the substrate and the bismuth oxygen selenium target is 50-60mm, and the laser sputtering energy density is 1-1.5Jcm -2 . Preferably, the conductive substrate and bismuth oxyseleniumThe distance between the targets is 55mm, preferably the oxygen pressure is 26Pa.
The beneficial effects of adopting above-mentioned scheme are: the proper oxygen pressure is used for adjusting the oxygen element proportion of the film, the enough laser energy density can sputter plasma plume to enable the film to grow on the substrate, and the distance between the conductive substrate and the bismuth oxygen selenium target can adjust the thickness of the film to enable the film to keep the thickness under the optimal catalytic activity.
Further, the pulse laser deposition system in the step (3) is filled with nitrogen gas with the atmosphere of 0.9x10 5 -1×10 5 Pa, taking out the composite electrode.
The beneficial effects of adopting above-mentioned scheme are: and nitrogen is filled in the cavity to protect the grown film, and the cavity door is opened to prepare the film.
An electrocatalytic moisture analysis oxygen reaction system comprises a working electrode, an auxiliary electrode, a reference electrode and electrolyte, wherein the working electrode is an amorphous bismuth oxygen selenium film composite electrode and a stainless steel electrode.
Further, the auxiliary electrode is a platinum wire electrode, the reference electrode is an Hg/HgO electrode, and the electrolyte is potassium hydroxide solution with the concentration of 0.1-1mol/L, preferably 1mol/L.
In summary, the invention has the following advantages:
1. the preparation method provided by the invention has the advantages that the sources of raw materials are rich, the glass carbon sheet and the bismuth oxygen selenium target material can be repeatedly used, the operation is simple and quick, the safety is high, the large-scale production is facilitated, the thickness of the film can be accurately regulated and controlled by adjusting the distance between the substrate and the bismuth oxygen selenium target material and the laser sputtering time length, so that the film thickness is controllable, and the performance is stable and the repeatability is high.
2. The amorphous bismuth oxygen selenium film composite electrode prepared by the invention can be directly used as a reaction electrode, has good conductivity, is not easy to corrode in electrolyte in an electrolytic water oxygen evolution reaction, and has good stability and high electrocatalytic activity.
3. The amorphous bismuth oxygen selenium film is different from a crystalline film, and has unordered crystal structure and relatively weak chemical bond energy, so that more active sites can be provided for electrochemical reaction in the chemical reaction process.
4. The amorphous bismuth oxygen selenium film can be well connected with a stainless steel electrode by using glassy carbon as a supporting substrate.
5. The amorphous bismuth oxygen selenium film composite electrode provided by the invention is applied to an electrocatalytic water analysis oxygen reaction system, and can effectively catalyze and promote the electrolytic water oxygen analysis reaction.
6. The amorphous bismuth oxyselenium is deposited and grown on the glassy carbon substrate through the laser pulse, the obtained electrode material has high binding force and good stability, and in addition, the amorphous bismuth oxyselenium can induce a self-adaptive process so as to promote electrochemical reaction.
7. The invention shows that the amorphous structure engineering can be an effective and general strategy for designing the next generation of electrolytic water oxygen evolution reaction to apply high-performance catalysts.
Drawings
FIG. 1 is a cyclic voltammogram of catalytic activity of OER reaction of the amorphous bismuth oxyselenium thin film composite electrode prepared in example 1;
FIG. 2 is a linear voltammogram of the catalytic activity of the amorphous bismuth oxyselenium thin film composite electrode OER reaction prepared in example 1;
FIG. 3 is a cyclic voltammogram of the double-layer capacitor of the amorphous bismuth oxyselenium thin film composite electrode prepared in example 1;
FIG. 4 is a schematic diagram of an electric double layer capacitor of the crystalline bismuth oxyselenium thin film composite electrode prepared in non-example 1;
FIG. 5 is a graph showing the current density change of the amorphous bismuth oxide selenium thin film composite electrode prepared in example 1 within 1000 seconds.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are provided to illustrate the invention and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the amorphous bismuth oxygen selenium film composite electrode comprises the following steps:
(1) Preparation of bismuth oxygen selenium target material
Fully mixing and grinding bismuth oxide and bismuth selenide powder with the purity of 99.9 percent according to a proportion, putting into a mould with the radius and the height of 5mm, pressing into a columnar body, sintering at the high temperature of 680 ℃ for 12 hours, and preparing a bismuth-oxygen-selenium target material, wherein the mol ratio of bismuth, oxygen and selenium atoms in the target material is 2:2:1;
(2) Substrate pretreatment
Polishing a 10mm multiplied by 10mm glass carbon sheet to be smooth by using alumina polishing powder with the diameter of 50nm, sequentially carrying out ultrasonic treatment on the glass carbon sheet by using acetone, absolute ethyl alcohol and deionized water for 10min respectively, and drying by using a nitrogen gun for standby after ultrasonic cleaning;
(3) Preparation of composite electrode
Placing the treated glass carbon sheet and bismuth oxygen selenium target material on a sample stage of a pulse laser deposition system, wherein the distance between a glass carbon sheet substrate and the bismuth oxygen selenium target material is 55mm, shielding the glass carbon sheet substrate by a baffle plate, and pumping the vacuum degree in a cavity to 2.0 multiplied by 10 -4 Pa, under vacuum environment and laser energy density of 1.5Jcm -2 Under the condition, pre-sputtering the bismuth oxygen selenium target material for 5min by using a laser pulser; after the pre-sputtering is completed, removing the baffle plate, and performing laser sputtering deposition on the glass carbon plate substrate for 14min; after the laser deposition is completed, nitrogen is filled into the cavity until the pressure in the cavity is 1 multiplied by 10 5 And taking out the sample after Pa to obtain the amorphous bismuth oxygen selenium film composite electrode.
The amorphous bismuth oxygen selenium film composite electrode prepared in the embodiment is used for preparing an OER electro-catalytic system, and the preparation method comprises the following steps:
and connecting the amorphous bismuth oxygen selenium film composite electrode with a stainless steel electrode to serve as a working electrode, then assembling the working electrode, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode into electrolyte which is 1mol/L potassium hydroxide solution, and connecting the electrolyte with an electrochemical workstation to obtain the OER electrocatalytic system.
Test examples
The amorphous bismuth oxyselenium thin film composite electrode prepared in example 1 was tested for cyclic voltammogram, linear voltammogram and cyclic voltammogram of electric double layer capacitor by OER catalytic system, as shown in fig. 1, fig. 2 and fig. 3, respectively. Wherein the cyclic voltammogram is tested using an OER catalytic system at a potential of 0.9 to 1.8 volts for reversible hydrogen electrodes at a scan rate of 50mV/s and the linear voltammogram is tested using an OER catalytic system at a potential of 0.9 to 1.9 volts for reversible hydrogen electrodes at a scan rate of 50mV/s. For the cyclic voltammogram of the double layer capacitor, the potential of the reversible hydrogen electrode was measured at 0.92 to 1.03 volts, and the scan rate was varied in a gradient from 80mV/s to 180mV/s, every 20 mV/s. The electric double layer capacitor schematic (as shown in fig. 4) is plotted by selecting the current density at a potential of 1.1 volts in the cyclic voltammogram of the electric double layer capacitor, and the slope thereof is the electric double layer capacitor value. The control potential was kept at 1.4V and the change in current density was tested, and the result is shown in fig. 5.
As can be seen from FIG. 1, the current density can be as high as 0.31mA/cm when tested by cyclic voltammetry 2 The method comprises the steps of carrying out a first treatment on the surface of the The current density can reach 0.46mA/cm in the linear voltammetry test 2 As shown in fig. 2. It can be seen from fig. 1 and 2 that there is a higher current density at a lower potential, with better OER performance. As can be seen from fig. 3, the amorphous bismuth oxyselenium film has larger electrochemical active surface area, which indicates that the amorphous bismuth oxyselenium film has more surface active sites and high OER catalytic activity. As shown in FIG. 4, the current density at a potential of 1.1V in the cyclic voltammogram of the double layer capacitor was plotted with a slope of 0.46mF/cm for the double layer capacitor 2 . As is clear from FIG. 5, the current of the amorphous thin film was continuously increased by 10% to the maximum threshold (0.018 mA/cm in a test for 1000 seconds at a control potential of 1.4V 2 ) The film material prepared by the method is relatively stable in electrolyte and is not easy to corrode.
Example 2
The preparation method of the amorphous bismuth oxygen selenium film composite electrode comprises the following steps:
(1) Preparation of bismuth oxygen selenium target material
Fully mixing and grinding bismuth oxide and bismuth selenide powder with the purity of 99.9 percent according to a proportion, putting into a mould with the radius and the height of 5mm, pressing into a columnar body, sintering at the high temperature of 680 ℃ for 12 hours, and preparing a bismuth-oxygen-selenium target material, wherein the mol ratio of bismuth, oxygen and selenium atoms in the target material is 2:2:1;
(2) Substrate pretreatment
Polishing a 10mm multiplied by 10mm glass carbon sheet to be smooth by using alumina polishing powder with the diameter of 20nm, sequentially using acetone, absolute ethyl alcohol and deionized water to respectively ultrasonically treat the glass carbon sheet for 15min, and drying the glass carbon sheet by using a nitrogen gun for later use after ultrasonic cleaning;
(3) Preparation of composite electrode
Placing the treated glass carbon sheet and bismuth oxygen selenium target material on a sample stage of a pulse laser deposition system, wherein the distance between a glass carbon sheet substrate and the bismuth oxygen selenium target material is 50mm, shielding the glass carbon sheet substrate by a baffle plate, and pumping the vacuum degree in a cavity to 1.9 multiplied by 10 -4 Pa, under vacuum environment and laser energy density of 1.5Jcm -2 Under the condition, pre-sputtering the bismuth oxygen selenium target material for 5min by using a laser pulser; after the pre-sputtering is completed, removing the baffle plate, and performing laser sputtering deposition on the glass carbon plate substrate for 15min; after the laser deposition is completed, nitrogen is filled into the cavity until the pressure in the cavity is 1 multiplied by 10 5 And taking out the sample after Pa to obtain the amorphous bismuth oxygen selenium film composite electrode.
The amorphous bismuth oxygen selenium film composite electrode prepared in the example 2 is used for preparing an OER electro-catalytic system, and the preparation method comprises the following steps:
and connecting the amorphous bismuth oxygen selenium film composite electrode with a stainless steel electrode to serve as a working electrode, then assembling the working electrode, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode into electrolyte which is potassium hydroxide solution with the concentration of 0.1mol/L, and connecting the electrolyte with an electrochemical workstation to obtain the OER electrocatalytic system.
Example 3
The preparation method of the amorphous bismuth oxygen selenium film composite electrode comprises the following steps:
(1) Preparation of bismuth oxygen selenium target material
Fully mixing and grinding bismuth oxide and bismuth selenide powder with the purity of 99.9 percent according to the molar ratio of 2:2:1 of bismuth, oxygen and selenium atoms, putting into a die with the radius and the height of 5mm, pressing into a columnar body, and sintering for 12 hours at the high temperature of 680 ℃ to prepare the bismuth oxygen selenium target;
(2) Substrate pretreatment
Polishing a 10mm multiplied by 10mm glass carbon sheet to be smooth by using alumina polishing powder with the diameter of 100nm, sequentially using acetone, absolute ethyl alcohol and deionized water to respectively ultrasonically treat the glass carbon sheet for 20 minutes, and drying the glass carbon sheet by using a nitrogen gun for later use after ultrasonic cleaning;
(3) Preparation of composite electrode
Placing the treated glass carbon sheet and bismuth oxygen selenium target material on a sample stage of a pulse laser deposition system, wherein the distance between a glass carbon sheet substrate and the bismuth oxygen selenium target material is 60mm, shielding the glass carbon sheet substrate by a baffle plate, and pumping the vacuum degree in a cavity to 2.0x10 -4 Pa, under vacuum environment and laser energy density of 1.5Jcm -2 Under the condition, pre-sputtering the bismuth oxygen selenium target material for 5min by using a laser pulser; after the pre-sputtering is completed, removing the baffle plate, and performing laser sputtering deposition on the glass carbon plate substrate for 13min; after the laser deposition is completed, nitrogen is filled into the cavity until the pressure in the cavity is 1 multiplied by 10 5 And taking out the sample after Pa to obtain the amorphous bismuth oxygen selenium film composite electrode.
The amorphous bismuth oxygen selenium film composite electrode prepared in the example 3 is used for preparing an OER electro-catalytic system, and the preparation method comprises the following steps:
and connecting the amorphous bismuth oxygen selenium film composite electrode with a stainless steel electrode to serve as a working electrode, then assembling the working electrode, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode into electrolyte which is potassium hydroxide solution with the concentration of 0.5mol/L, and connecting the electrolyte with an electrochemical workstation to obtain the OER electrocatalytic system.
Comparative example 1
An OER electro-catalytic system comprises a working electrode, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode of a bismuth oxygen selenium monocrystal film, and the preparation method is the same as that of the OER electro-catalytic system in the embodiment 1. Tested by the method described in the test example in example 1, the highest current density was 0.15mA/cm 2 Compared with the OER electro-catalytic system prepared in example 1, the current density is only 30%, and the current density is drastically reduced after 130s, so that the OER performance and stability of the amorphous bismuth oxygen selenium film composite electrode prepared in the invention are higher than those of the single crystal bismuth oxygen selenium film composite electrodeHighlighting the significant advances in the technology of the present invention.
Although specific embodiments of the invention have been described in detail with reference to the accompanying drawings, it should not be construed as limiting the scope of protection of the present patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (8)
1. The application of the amorphous bismuth oxygen selenium film composite electrode in preparing an electrocatalytic moisture analysis oxygen reaction system is characterized in that the system comprises a working electrode, an auxiliary electrode, a reference electrode and electrolyte, wherein the working electrode comprises the amorphous bismuth oxygen selenium film composite electrode and a stainless steel electrode;
the preparation method of the amorphous bismuth oxygen selenium film composite electrode comprises the following steps:
(1) Preparation of bismuth oxygen selenium target material
Weighing bismuth oxide and bismuth selenide according to a proportion, mixing, grinding and sintering to prepare a bismuth oxygen selenium target material;
(2) Substrate pretreatment
Polishing and ultrasonic cleaning are sequentially carried out on the conductive substrate glassy carbon, and then inert gas is used for drying for standby;
(3) Preparation of composite electrode
Placing the bismuth oxygen selenium target material prepared in the step (1) and the substrate prepared in the step (2) in a pulse laser deposition system, carrying out pre-sputtering on the bismuth oxygen selenium target material under the conditions of a vacuum environment and constant laser energy density after vacuumizing, carrying out laser firing on the bismuth oxygen selenium target material after the pre-sputtering is finished, depositing the bismuth oxygen selenium target material on a conductive substrate, and taking out the bismuth oxygen selenium film under the nitrogen atmosphere to prepare the amorphous bismuth oxygen selenium film composite electrode.
2. The use of the amorphous bismuth oxygen selenium thin film composite electrode according to claim 1 for preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the molar ratio of bismuth, oxygen and selenium atoms in the bismuth oxygen selenium target material in the step (1) is 2:2:1.
3. The use of the amorphous bismuth oxygen selenium thin film composite electrode according to claim 1 for preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the sintering temperature in the step (1) is 600-680 ℃ and the sintering time is 10-14h.
4. The use of the amorphous bismuth oxygen selenium thin film composite electrode according to claim 1 for preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the ultrasonic cleaning process in the step (2) comprises the following steps: sequentially using acetone, absolute ethyl alcohol and deionized water to ultrasonically clean for 10-20min.
5. The use of the amorphous bismuth oxygen selenium thin film composite electrode according to claim 1 for preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the pressure in the deposition system after being pumped to vacuum in the step (3) is 1.0x10 -4 -3.0×10 -4 Pa。
6. The application of the amorphous bismuth oxygen selenium film composite electrode according to claim 1 in preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the pre-sputtering time in the step (3) is 3-5min, and the laser firing time is 10-15min; the distance between the substrate and the bismuth oxygen selenium target is 50-60mm, and the laser sputtering energy density is 1-1.5Jcm -2 。
7. The use of the amorphous bismuth oxygen selenium thin film composite electrode according to claim 1 for preparing an electrocatalytic moisture analysis oxygen reaction system, wherein the thin film is taken out in the nitrogen atmosphere in the step (3), and the nitrogen pressure is 0.9×10 5 -1×10 5 Pa。
8. The application of the amorphous bismuth oxygen selenium film composite electrode in preparing an electrocatalytic moisture analysis oxygen reaction system as claimed in claim 1, wherein the auxiliary electrode is a platinum wire electrode, the reference electrode is an Hg/HgO electrode, and the electrolyte is potassium hydroxide solution with the concentration of 0.1-1 mol/L.
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