CN114990613A - 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 84
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000008021 deposition Effects 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 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 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 25
- 238000004544 sputter deposition Methods 0.000 claims description 25
- 229910052797 bismuth Inorganic materials 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 125000004430 oxygen atom Chemical group O* 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 compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000861 blow drying Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000006555 catalytic reaction Methods 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
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 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
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- VQNPRYUMHLOITA-UHFFFAOYSA-N [Se]O Chemical compound [Se]O VQNPRYUMHLOITA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 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
- 238000001556 precipitation Methods 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
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- 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
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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 grinding the glassy carbon substrate by using alumina polishing powder, cleaning by using ultrasonic waves, and blow-drying by using inert gas; fixing the bismuth-oxygen-selenium film composite electrode on a sample table of a pulse laser deposition system, pre-burning the bismuth-oxygen-selenium film composite electrode under the conditions of background vacuum with certain pressure intensity and constant laser energy density, then taking down a baffle for deposition, and taking out a sample under the nitrogen atmosphere to obtain the bismuth-oxygen-selenium film composite electrode. The amorphous bismuth oxygen selenium film composite electrode is applied to an electrocatalytic water-splitting oxygen-analyzing reaction system, and can effectively catalyze and promote the implementation of the electrolyzed water-splitting oxygen-analyzing reaction. The invention shows that the amorphous structure engineering can become an effective and general strategy for designing a high-performance catalyst applied to the next generation of electrolytic water oxygen evolution reaction.
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 modern society, due to excessive exploitation of fossil energy and increasingly worsened ecological environment, development of new clean energy is not slow. The electrochemical reaction is 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 electrolyzed water is huge, the energy stored in the electrolyzed water also becomes an important development trend, the purity of the gas produced by the electrolyzed water is almost 100%, and the electrolyzed water is non-toxic and pollution-free. However, even with the most advanced catalysts, oxygen electrocatalysis severely limits the energy efficiency and rate capability of electrochemical energy devices due to the large overpotentials required to drive the reaction. The promotion of oxygen half-reactions 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 2 The catalyst is considered to be the catalyst with the strongest catalysis activity in Oxygen Evolution Reaction (OER), but the two catalysts have poor stability in the reaction process and are expensive, so that the catalyst cannot be applied to commercial and industrial production on a large scale. Research has shown that in recent years, high-symmetry phase selenium oxide has proven to be an electrocatalyst for promoting OER in alkaline solutions with high activity and stability and at low cost, compared to expensive and scarce noble metal catalysts.
The bismuth-oxygen-selenium film only has a small amount of research in the field of OER catalytic performance, and the amorphous bismuth-oxygen-selenium film covered glassy carbon sheet has better catalytic activity and stability in an alkaline solution, and can effectively catalyze and promote the OER reaction.
Disclosure of Invention
At present, a bismuth-oxygen-selenium film is used as an OER catalyst, and when oxygen precipitation reaction occurs, a large amount of oxygen is generated on the surface of the catalyst, so that the catalyst is corroded, and the serious consequence of catalyst decomposition is caused. Meanwhile, the introduction of organic components such as adhesives can cover part of active sites on the surface of the catalyst, so that the partial deactivation of the catalyst is caused, 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 and a preparation method and application thereof, which can solve the problems that a bismuth-oxygen-selenium film is not easy to directly participate in electrocatalytic reaction, is easy to corrode and fall off in the reaction process, and has low catalytic activity due to few active sites.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of an 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
Sequentially polishing and ultrasonically cleaning the conductive substrate glassy carbon, and then drying the conductive substrate glassy carbon by inert gas for later use;
(3) preparation of composite electrode
And (3) placing the bismuth-oxygen-selenium target material prepared in the step (1) and the substrate in the step (2) in a pulse laser deposition system, vacuumizing, pre-sputtering the bismuth-oxygen-selenium target material in a vacuum environment under the condition of constant laser energy density, performing 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 in a nitrogen atmosphere to prepare the amorphous bismuth-oxygen-selenium film composite electrode.
The beneficial effect who adopts above-mentioned scheme is: firstly, preparing a bismuth-oxygen-selenium target material, wherein the bismuth-oxygen-selenium target material is sintered 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 glassy carbon sheet to enable the surface of the glassy carbon sheet to be flat and smooth, so that the bismuth-oxygen-selenium film can be conveniently covered, the prepared bismuth-oxygen-selenium amorphous film is conductive, and needs to be conducted with a stainless steel electrode when used for catalyzing OER reaction, so that the glassy carbon sheet with better conductivity is needed to be used as a substrate. Impurities on the surface of the target material can be removed by carrying out pre-sputtering treatment on the bismuth-oxygen-selenium target material, deposition is carried out at room temperature to enable the grown film to be amorphous, the film is grown through a pulse laser sputtering deposition system, and when laser is applied to the target material, the film is grownGenerating a plasma, the plasma adhering to the substrate SrTiO 3 Forming a film on the substrate to prepare the amorphous bismuth-oxygen-selenium film composite electrode.
Further, the molar ratio of bismuth atoms, oxygen atoms and selenium atoms in the bismuth-oxygen-selenium target material in the step (1) is 2:2: 1.
The beneficial effect who adopts above-mentioned scheme is: the molar ratio of bismuth atoms to oxygen atoms to selenium atoms in the bismuth-oxygen-selenium target material is 2:2:1 so as to ensure the stoichiometric ratio of the target material.
Further, the sintering temperature in the step (1) is 600-680 ℃, and the sintering time is 10-14 h. The sintering temperature is preferably 680 ℃, and the sintering time is preferably 12 h.
The beneficial effect who adopts above-mentioned scheme is: the sintering time is long, the sintering temperature is high, bismuth oxide and bismuth selenide powder can fully react to generate the bismuth-oxygen-selenium target material, and the target material can be repeatedly used.
Further, the grinding and ultrasonic cleaning process in the step (2) comprises the following steps: firstly, the surface and the periphery of the glassy carbon plate are fully polished by using alumina polishing powder with the diameter of 20-200 nm. Then ultrasonic cleaning is carried out for 10-20min by using acetone, absolute ethyl alcohol and deionized water respectively in sequence. The diameter of the alumina polishing powder is preferably 50nm, and the ultrasonic cleaning time is preferably 15 min.
The beneficial effect who adopts above-mentioned scheme is: the aluminum oxide polishing powder is fully polished, so that the surface of the glassy carbon sheet is flat and smooth enough, the subsequent bismuth-oxygen-selenium film covering is facilitated, and the glassy carbon sheet can be recycled. The acetone can clean organic impurities on the glassy carbon sheet, the anhydrous ethanol can clean acetone remained on the glassy carbon sheet, and the deionized water can clean ethanol and other inorganic matters remained on the glassy carbon sheet.
Further, the pressure in the deposition system after the vacuum pumping in the step (3) is 1.9X 10 -4 -2.0×10 -4 Pa. The preferred vacuum pressure is 1.9X 10 -4 Pa。
The beneficial effect who adopts above-mentioned scheme is: the vacuum degree is low enough to ensure that the 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 28-32 min. Preferably, the pre-sputtering time is 5min, and the laser sputtering time is 30 min.
The beneficial effect who adopts above-mentioned scheme is: the impurities on the surface of the target material are removed by pre-sputtering, the film is not interfered by the impurities on the surface of the target material when being deposited, and the thickness of the film can be adjusted by the laser sputtering time, so that the film can keep the thickness under the optimal catalytic activity.
Further, in the step (3), the distance between the conductive substrate and the bismuth-oxygen-selenium target material is 50-60mm, and the oxygen pressure in the growth process is 1-30 Pa; the distance between the substrate and the bismuth-oxygen-selenium target material is 50-60mm, and the laser sputtering energy density is 1-1.5Jcm -2 . The distance between the conductive substrate and the bismuth-oxygen-selenium target is preferably 55mm, and the oxygen pressure is preferably 26 Pa.
The beneficial effect who adopts above-mentioned scheme is: the proper oxygen pressure is used for adjusting the oxygen element proportion of the film, the sufficient 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, so that the film can keep the thickness under the optimal catalytic activity.
Further, the nitrogen atmosphere filled into the pulse laser deposition system in the step (3) is 0.9 multiplied by 10 5 -1×10 5 Pa, taking out the composite electrode.
The beneficial effect who adopts above-mentioned scheme is: and (4) filling nitrogen to protect the grown film, and opening the cavity door to obtain the film.
An electrocatalytic water decomposition oxygen analysis 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.
Furthermore, the auxiliary electrode is a platinum wire electrode, the reference electrode is an Hg/HgO electrode, and the electrolyte is a potassium hydroxide solution with the concentration of 0.1-1mol/L, preferably 1 mol/L.
In summary, the invention has the following advantages:
1. the preparation method provided by the invention has the advantages that the raw material sources are rich, the glassy carbon sheet and the bismuth-oxygen-selenium target material can be repeatedly used, the operation is simple, convenient 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 duration, the thickness of the film is controllable, 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 the electrolytic water oxygen evolution reaction, has good stability and high electrocatalytic activity.
3. The amorphous bismuth oxyselem film is different from the crystalline film, and due to disordered crystal structure and relatively weak chemical bond energy, more active sites can be provided for electrochemical reaction in the chemical reaction process.
4. The amorphous bismuth oxyselem 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 decomposition oxygen analysis reaction system, and can effectively catalyze and promote the electrolytic water decomposition oxygen analysis reaction.
6. The amorphous bismuth oxyselem is deposited and grown on the glassy carbon substrate through laser pulse, the obtained electrode material is high in binding force and good in stability, and in addition, the amorphous bismuth oxyselem can induce a self-adaptive process to promote electrochemical reaction.
7. The invention shows that the amorphous structure engineering can become an effective and general strategy for designing a high-performance catalyst applied to the next generation of electrolytic water oxygen evolution reaction.
Drawings
FIG. 1 is a cyclic voltammetry curve of the OER reaction catalytic activity of the amorphous bismuth oxyselenium thin film composite electrode prepared in example 1;
FIG. 2 is a linear voltammogram of the OER reaction catalytic activity of the amorphous bismuth oxyselen thin film composite electrode prepared in example 1;
FIG. 3 is a cyclic voltammogram of the double layer capacitance of the amorphous bismuth oxyselem thin film composite electrode prepared in example 1;
FIG. 4 is a schematic diagram of the double layer capacitance of a composite electrode of a bismuth-oxide-selenium thin film prepared in non-example 1;
FIG. 5 is a graph showing the current density variation of the amorphous bismuth oxyselem thin film composite electrode prepared in example 1 within 1000 s.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
A preparation method of an 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 powder with the purity of 99.9 percent and bismuth selenide powder according to a proportion, putting the mixture into a mould with the radius and height of 5mm to press the mixture into a columnar body, sintering the columnar body at the high temperature of 680 ℃ for 12 hours to prepare the bismuth-oxygen-selenium target material, wherein the molar ratio of bismuth atoms to oxygen atoms to selenium atoms in the target material is 2:2: 1;
(2) substrate pretreatment
Polishing a glassy carbon sheet with the size of 10mm multiplied by 10mm smoothly by using alumina polishing powder with the diameter of 50nm, then respectively carrying out ultrasonic treatment on the glassy carbon sheet for 10min by sequentially using acetone, absolute ethyl alcohol and deionized water, and drying the glassy carbon sheet for later use by using a nitrogen gun after ultrasonic cleaning;
(3) preparation of composite electrode
Placing the processed glassy carbon sheet and the bismuth-oxygen-selenium target material on a sample table of a pulse laser deposition system, wherein the distance between a glassy carbon sheet substrate and the bismuth-oxygen-selenium target material is 55mm, shielding the glassy carbon sheet substrate by a baffle, and pumping the vacuum degree in a cavity to 2.0 multiplied by 10 -4 Pa, in vacuum environment and laser energy density of 1.5Jcm -2 Under the condition, pre-sputtering the bismuth-oxygen-selenium target for 5min by using a laser pulser; after the pre-sputtering is finished, the baffle is removed, and the laser sputtering deposition is carried out on the glassy carbon substrate for 14 min; after the laser deposition is finished, nitrogen is filled until the pressure in the cavity is 1 multiplied by 10 5 And after Pa, taking out the sample to prepare 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-catalysis 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 be used as a working electrode, assembling the working electrode, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode into an electrolyte, wherein the electrolyte is a potassium hydroxide solution with the concentration of 1mol/L, and connecting the electrolyte with an electrochemical workstation to obtain the OER electro-catalysis system.
Test examples
Cyclic voltammograms, linear voltammograms, and cyclic voltammograms of electric double layer capacitance were measured using the OER catalytic system on the amorphous bismuth oxysele thin film composite electrode prepared in example 1, as shown in fig. 1, 2, and 3, respectively. Wherein the cyclic voltammetry curve is tested at a potential of 0.9 to 1.8 volts for the reversible hydrogen electrode using the OER catalytic system at a scan rate of 50mV/s, and the linear voltammetry curve is tested at a potential of 0.9 to 1.9 volts for the reversible hydrogen electrode using the OER catalytic system at a scan rate of 50 mV/s. For cyclic voltammograms of the double layer capacitance, the scan rate was measured at a potential of 0.92 to 1.03 volts at the reversible hydrogen electrode and varied in a gradient from 80mV/s to 180mV/s every 20 mV/s. In the schematic diagram of the electric double layer capacitance (as shown in fig. 4), the current density at a potential of 1.1 v in the cyclic voltammetry curve of the electric double layer capacitance is selected and plotted, and the slope is the electric double layer capacitance. The control potential was kept at 1.4V, and the change in current density was measured, and the results are shown in fig. 5.
As can be seen from FIG. 1, the current density can be as high as 0.31mA/cm when the cyclic voltammetry is used for testing 2 (ii) a When the linear voltammetry test is carried out, the current density can reach 0.46mA/cm 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 electrochemical active surface area of the amorphous bismuth oxyselem film is large, which indicates that the film has many 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 electric double layer capacitor was plotted, and the slope thereof was 0.46mF/cm in the electric double layer capacitance value 2 . As can be seen from FIG. 5, at a control potential of 1.4V, the current of the amorphous thin film continuously increased by 10% in a test of 1000s to reach the maximum threshold value (0.018 mA/cm) 2 ) The results show that the film material prepared by the invention is relatively stable in the electrolyte and is not easy to corrode.
Example 2
A preparation method of an 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 powder with the purity of 99.9 percent and bismuth selenide powder according to a proportion, putting the mixture into a mould with the radius and height of 5mm to press the mixture into a columnar body, sintering the columnar body at the high temperature of 680 ℃ for 12 hours to prepare the bismuth-oxygen-selenium target material, wherein the molar ratio of bismuth atoms to oxygen atoms to selenium atoms in the target material is 2:2: 1;
(2) substrate pretreatment
Polishing a glassy carbon sheet with the size of 10mm multiplied by 10mm smoothly by using aluminum oxide polishing powder with the diameter of 20nm, then sequentially performing ultrasonic treatment on the glassy carbon sheet for 15min by using acetone, absolute ethyl alcohol and deionized water respectively, and performing ultrasonic cleaning and blow-drying by using a nitrogen gun for later use;
(3) preparation of composite electrode
Placing the processed glassy carbon sheet and the bismuth-oxygen-selenium target material on a sample table of a pulse laser deposition system, wherein the distance between a glassy carbon sheet substrate and the bismuth-oxygen-selenium target material is 50mm, shielding the glassy carbon sheet substrate by a baffle, and pumping the vacuum degree in a cavity to 1.9 multiplied by 10 -4 Pa, 1.5Jcm in vacuum environment and laser energy density -2 Under the condition, a laser pulser is used for pre-sputtering the bismuth-oxygen-selenium target material for 5 min; after the pre-sputtering is finished, the baffle is removed, and laser sputtering deposition is carried out on the glassy carbon substrate for 15 min; after the laser deposition is finished, nitrogen is filled until the pressure in the cavity is 1 multiplied by 10 5 And after Pa, taking out the sample to prepare 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-catalysis system, and the preparation method comprises the following steps:
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 an electrolyte, wherein the electrolyte is a potassium hydroxide solution with the concentration of 0.1mol/L, and connecting an electrochemical workstation to obtain the OER electro-catalysis system.
Example 3
A preparation method of an 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 powder with the purity of 99.9% and bismuth selenide powder according to the molar ratio of bismuth atoms to oxygen atoms to selenium atoms of 2:2:1, putting the mixture into a mold with the radius and height of 5mm to press the mixture into a columnar body, and sintering the columnar body at the high temperature of 680 ℃ for 12 hours to prepare the bismuth-oxygen-selenium target material;
(2) substrate pretreatment
Polishing a glassy carbon sheet with the size of 10mm multiplied by 10mm smoothly by using alumina polishing powder with the diameter of 100nm, then respectively carrying out ultrasonic treatment on the glassy carbon sheet for 20min by using acetone, absolute ethyl alcohol and deionized water in sequence, and drying the glassy carbon sheet for later use by using a nitrogen gun after ultrasonic cleaning;
(3) preparation of composite electrode
Placing the processed glassy carbon sheet and bismuth-oxygen-selenium target material on a sample table of a pulse laser deposition system, wherein the distance between the base of the glassy carbon sheet and the bismuth-oxygen-selenium target material is 60mm, shielding the substrate of the glassy carbon sheet by a baffle plate, and pumping the vacuum degree in a cavity to 2.0 multiplied by 10 -4 Pa, 1.5Jcm in vacuum environment and laser energy density -2 Under the condition, pre-sputtering the bismuth-oxygen-selenium target for 5min by using a laser pulser; after the pre-sputtering is finished, the baffle is removed, and laser sputtering deposition is carried out on the glassy carbon substrate for 13 min; after the laser deposition is finished, nitrogen is filled until the pressure in the cavity is 1 multiplied by 10 5 And after Pa, taking out the sample to prepare the amorphous bismuth oxygen selenium film composite electrode.
The amorphous bismuth-oxygen-selenium film composite electrode prepared in the embodiment 3 is used for preparing an OER electro-catalysis system, and the preparation method comprises the following steps:
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 an electrolyte, wherein the electrolyte is a potassium hydroxide solution with the concentration of 0.5mol/L, and connecting the electrolyte with an electrochemical workstation to obtain the OER electro-catalysis system.
Comparative example 1
An OER electro-catalysis system comprises a working electrode of a bismuth-oxygen-selenium single crystal film, an auxiliary electrode platinum wire electrode and a reference electrode Hg/HgO electrode, and the preparation method is consistent with that of the OER electro-catalysis system in the embodiment 1. The highest current density was 0.15mA/cm as measured by the method described in test example 1 2 Compared with the OER electrocatalysis system prepared in the embodiment 1, the current density is only 30%, and the current density is sharply reduced after 130s, so that the OER performance and stability of the amorphous bismuth-oxygen-selenium film composite electrode prepared by the invention are higher than those of a single-crystal bismuth-oxygen-selenium film composite electrode, and the technology of the invention is remarkably improved.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive work within the scope of the appended claims.
Claims (10)
1. The preparation method of the amorphous bismuth-oxygen-selenium film composite electrode is characterized by comprising the following steps of:
(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
Sequentially polishing and ultrasonically cleaning the conductive substrate glassy carbon, and then drying the conductive substrate glassy carbon by inert gas for later use;
(3) preparation of composite electrode
And (3) placing the bismuth-oxygen-selenium target material prepared in the step (1) and the substrate in the step (2) in a pulse laser deposition system, vacuumizing, pre-sputtering the bismuth-oxygen-selenium target material in a vacuum environment under the condition of constant laser energy density, performing 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 in a nitrogen atmosphere to prepare the amorphous bismuth-oxygen-selenium film composite electrode.
2. The method for preparing the amorphous bismuth-oxygen-selenium film composite electrode as claimed in claim 1, wherein the molar ratio of bismuth atoms to oxygen atoms to selenium atoms in the bismuth-oxygen-selenium target material in the step (1) is 2:2: 1.
3. The method for preparing the amorphous bismuth oxyselem thin film composite electrode of claim 1, wherein the sintering temperature in the step (1) is 600-680 ℃, and the sintering time is 10-14 h.
4. The method for preparing the amorphous bismuth oxyselem film composite electrode of claim 1, wherein the ultrasonic cleaning process in the step (2) comprises the following steps: and ultrasonic cleaning with acetone, anhydrous ethanol and deionized water for 10-20 min.
5. The method for preparing the amorphous bismuth oxyselem thin film composite electrode of claim 1, wherein the pressure in the deposition system after the evacuation in the step (3) is 1.0 x 10 -4 -3.0×10 -4 Pa。
6. The method for preparing the amorphous bismuth oxyselem film composite electrode of claim 1, wherein the pre-sputtering time in the step (3) is 3-5min, and the laser burning time is 10-15 min; the distance between the substrate and the bismuth-oxygen-selenium target material is 50-60mm, and the laser sputtering energy density is 1-1.5Jcm -2 。
7. The method for preparing the amorphous bismuth oxyselem film composite electrode of claim 1, wherein in the step (3), the film is taken out in a nitrogen atmosphere with a nitrogen pressure of 0.9 x 10 5 -1×10 5 Pa。
8. An amorphous bismuth oxyselem thin film composite electrode prepared according to the method of any one of claims 1 to 7.
9. The use of the amorphous bismuth oxyselem thin film composite electrode according to claim 8 for preparing an electrocatalytic oxygen evolution reaction system, wherein the system comprises a working electrode, an auxiliary electrode, a reference electrode and an electrolyte, wherein the working electrode comprises the amorphous bismuth oxyselem thin film composite electrode and a stainless steel electrode.
10. The use of the amorphous bismuth oxyselem thin film composite electrode of claim 9 for preparing an electrocatalytic oxygen analysis reaction system, wherein the auxiliary electrode is a platinum wire electrode, the reference electrode is a Hg/HgO electrode, and the electrolyte is a potassium hydroxide solution with a concentration of 0.1-1 mol/L.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438567A (en) * | 2019-07-22 | 2019-11-12 | 中国科学院上海微系统与信息技术研究所 | A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material |
| CN112588303A (en) * | 2020-11-23 | 2021-04-02 | 安徽大学 | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on preparation method |
| CN113000054A (en) * | 2021-03-30 | 2021-06-22 | 广州大学 | Bi2O2Preparation method of Se material |
| CN113073353A (en) * | 2021-03-26 | 2021-07-06 | 电子科技大学 | Amorphous lanthanum nickelate film composite electrode and preparation method and application thereof |
| CN113804294A (en) * | 2021-09-15 | 2021-12-17 | 哈尔滨工业大学 | Preparation method of self-powered photoelectric detector of bismuth-oxygen-selenium nanosheets |
| CN113897634A (en) * | 2021-11-09 | 2022-01-07 | 电子科技大学长三角研究院(湖州) | Amorphous strontium ruthenate film composite electrode and preparation method and application thereof |
-
2022
- 2022-04-07 CN CN202210365309.5A patent/CN114990613B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438567A (en) * | 2019-07-22 | 2019-11-12 | 中国科学院上海微系统与信息技术研究所 | A kind of preparation method of semiconductor selenium bismuth oxide single crystal thin-film material |
| CN112588303A (en) * | 2020-11-23 | 2021-04-02 | 安徽大学 | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on preparation method |
| CN113073353A (en) * | 2021-03-26 | 2021-07-06 | 电子科技大学 | Amorphous lanthanum nickelate film composite electrode and preparation method and application thereof |
| CN113000054A (en) * | 2021-03-30 | 2021-06-22 | 广州大学 | Bi2O2Preparation method of Se material |
| CN113804294A (en) * | 2021-09-15 | 2021-12-17 | 哈尔滨工业大学 | Preparation method of self-powered photoelectric detector of bismuth-oxygen-selenium nanosheets |
| CN113897634A (en) * | 2021-11-09 | 2022-01-07 | 电子科技大学长三角研究院(湖州) | Amorphous strontium ruthenate film composite electrode and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOYANG WANG等: ""Decoration of Bi2Se3 nanosheets with a thin Bi2SeO2 layer for visible-light-driven overall water splitting"" * |
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