CN111359603A - Bismuth-based self-supporting electrocatalyst, preparation method thereof and application of bismuth-based self-supporting electrocatalyst in ammonia production by nitrogen reduction - Google Patents
Bismuth-based self-supporting electrocatalyst, preparation method thereof and application of bismuth-based self-supporting electrocatalyst in ammonia production by nitrogen reduction Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 24
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 238000002848 electrochemical method Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000003100 immobilizing effect Effects 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229940075397 calomel Drugs 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a bismuth-based self-supporting electrocatalyst and application of the bismuth-based self-supporting electrocatalyst in production of ammonia by electrocatalysis of nitrogen reduction. Electrochemically immobilizing Bi on an electrochemically treated carbon material substrate2O3Catalyst nanoparticles to obtain the bismuth-based self-supporting electrocatalyst. The carbon material treated by the electrochemical method is used as a working electrode, a platinum sheet electrode is used as a counter electrode and a reference electrodeVery much of BiCl3The obtained ethylene glycol solution is used as an electrolyte to carry out electrodeposition, and the obtained Bi is supported2O3And taking out the carbon material substrate of the catalyst nano-particles, cleaning and drying to obtain the bismuth-based self-supporting electrocatalyst. The invention obtains the bismuth-based self-supporting electro-catalytic material with stable structure, good conductivity and large specific surface area. The preparation method is simple, has good repeatability, does not need a binder, has adjustable solid loading capacity, has ideal ammonia production efficiency and Faraday efficiency of electro-catalysis nitrogen reduction, and has wide application prospect in the fields of electro-catalysis nitrogen reduction for producing ammonia and the like.
Description
Technical Field
The invention belongs to the field of catalyst materials, and particularly relates to preparation of a bismuth-based self-supporting electrocatalyst with catalytic performance on ammonia production by nitrogen reduction and application of the bismuth-based self-supporting electrocatalyst in an electrocatalysis reaction of ammonia production by nitrogen reduction.
Background
Ammonia (NH)3) Is one of the most important chemical raw materials in the current human society, and plays a very important role in the fields of agriculture, industry, textile industry and the like. The ammonia gas is easy to liquefy, store and transport, has high energy density (4.32KWh/L), has the hydrogen content of 17.6 wt%, is a very stable hydrogen energy carrier, and can be dissociated into hydrogen gas. The demand of the modern society for ammonia gas is increasing day by day, but at present, the ammonia is produced industrially mainly by the traditional Haber-Bosch method, which is harsh (high temperature and high pressure), heavy in pollution (large amount of carbon dioxide emission), and high in energy consumption (energy consumption in the production process accounts for about 1% of energy consumption in the world year). In recent years, with the proposal of the concept of green sustainable development, the development of a method for producing ammonia with green sustainable development is not slow. The electrocatalytic nitrogen reduction method is to convert nitrogen and water into ammonia gas by electric energy at normal temperature and normal pressure. Research shows that bismuth oxide has good response to ammonia produced by nitrogen reduction. Compared with the traditional carbon paper, the peeled carbon paper has the advantages of large specific surface area, more immobilization sites, large interlayer spacing and the like, and can adjust the immobilization amount of the bismuth oxide nano particles. Therefore, the bismuth oxide nano particles are immobilized on the stripping carbon paper, and have higher catalytic activity than the bismuth oxide immobilized on the traditional carbon paper, so that the development of the technology for producing ammonia by electrocatalysis nitrogen reduction is greatly promoted.
Disclosure of Invention
The invention aims to provide a preparation method of a bismuth-based self-supporting electrocatalyst with simple preparation method, good repeatability, no binder and adjustable solid loading.
In order to achieve the purpose, the invention adopts the technical scheme that: a bismuth-based self-supporting electrocatalyst is prepared by electrochemically immobilizing Bi on a carbon material substrate treated by an electrochemical method2O3The bismuth-based self-supporting electrocatalyst is obtained by using the catalyst nanoparticles.
Preferably, in the bismuth-based self-supporting electrocatalyst described above, the carbon material substrate is carbon paper.
Preferably, the preparation method of the bismuth-based self-supporting electrocatalyst comprises the following steps: performing electrodeposition with salt solution of bismuth as electrolyte under constant current density by using carbon paper treated by electrochemical method as working electrode, platinum sheet electrode as counter electrode and reference electrode, and the obtained immobilized Bi2O3Taking out the carbon material substrate of the catalyst nano-particles, washing with ethanol for a plurality of times, and drying in vacuum to obtain the bismuth-based self-supporting electrocatalyst Bi2O3@FEG。
Preferably, in the preparation method of the bismuth-based self-supporting electrocatalyst, the current density of the electrodeposition is 1mA cm-2The time of electrodeposition is 5-10 min.
Preferably, the preparation method of the bismuth-based self-supporting electrocatalyst, the carbon paper treated by the electrochemical method, comprises the following steps: the carbon paper is used as a working electrode, a calomel electrode is used as a reference electrode, the other piece of carbon paper is used as a counter electrode, the carbon paper is treated in a range of 0.6 to 1.8V by CV, soaked in deionized water for 12h, cleaned for a plurality of times by deionized water after passing through 8000 s and 10000s at i-t constant voltage, treated in a range of-1 to 0.9V by CV, cleaned for a plurality of times by clear water, freeze-dried for 6h, and then vacuum-dried for 12h in a vacuum drying box, so that the carbon paper FEG treated by the electrochemical method is obtained.
Preferably, in the preparation method of the bismuth-based self-supporting electrocatalyst, the electrolyte is BiCl3A glycol solution of (a); the preparation method comprises the following steps: adding BiCl3Adding into ethylene glycol, stirring for 1h at room temperature to obtain BiCl3The ethylene glycol solution of (1).
Preferably, the BiCl is prepared by the method for preparing the bismuth-based self-supporting electrocatalyst3The concentration of the ethylene glycol solution is 0.2-0.5mol L-1。
The application of the bismuth-based self-supporting electrocatalyst in electrocatalysis of nitrogen reduction to produce ammonia.
Preferably, the above application, method is as follows: h-type electrolytic cell is used as electrolytic bath, Na is used2SO4The solution is used as electrolyte, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and Bi is added2O3The @ FEG clamp was placed on a platinum electrode clamp and used directly as the working electrode. And carrying out electrocatalytic nitrogen reduction to produce ammonia in a nitrogen atmosphere.
The invention has the beneficial effects that: the invention provides a simple and feasible method for preparing a high-efficiency bismuth-based catalyst, the method has universality in preparing a bismuth-based catalyst material with carbon paper as a substrate, and the catalyst Bi prepared by the method of the invention2O3The @ FEG can be efficiently recycled in a catalytic system, a binder is not needed in preparation, the interlayer spacing is high, the specific surface area is large, the catalytic efficiency of the catalyst is further improved, and the solid loading amount of the bismuth oxide catalyst nanoparticles can be adjusted by changing the concentration and the deposition time of the electrodeposition electrolyte. The catalyst material prepared by the method has good application prospect in the aspect of electro-catalysis of nitrogen reduction to produce ammonia.
Description of the drawings:
FIG. 1 shows Bi prepared in example 12O3SEM image of @ FEG.
FIG. 2 shows Bi prepared in example 12O3The TEM image of @ FEG.
FIG. 3 shows Bi prepared in example 12O3Scheme for synthesis of @ FEG.
FIG. 4 shows the electrocatalyst Bi according to example 22O3@ FEG is an ammonia production efficiency map for nitrogen reduction to produce ammonia.
FIG. 5 shows the electrocatalyst Bi according to example 22O3@ FEG is a Faraday efficiency plot for nitrogen reduction to ammonia.
FIG. 6 shows the electrocatalyst Bi according to example 22O3@ FEG Ammonia production efficiency plot for repeatability test of nitrogen reduction ammonia production.
FIG. 7 shows Bi prepared in example 12O3The XRD pattern of @ FEG.
Detailed Description
Example 1 bismuth-based self-supporting electrocatalyst (Bi)2O3@FEG)
The preparation method comprises the following steps:
1) preparation of FEG: carbon paper is used as a working electrode, a calomel electrode is used as a reference electrode, and the other piece of carbon paper is used as a counter electrode. First, the carbon paper is passed through a CV at a voltage range of 0.6 to 1.8V at 20mV s-1Sweep at a sweep rate of 8 cycles, 25mL0.5 mol L-1K2CO3The solution is used as electrolyte and soaked in deionized water for 12 h. The carbon paper was then swept by i-t at 1.8V constant voltage for 9000s at 25mL0.5 mol L-1KNO3The solution is used as electrolyte and is washed with deionized water for several times. Finally, the carbon paper was passed through the CV at a voltage range of-1 to 0.9V with 50mV s-1Sweeping 50 circles at a sweeping speed of 25mL3 mol L-1K2CO3The solution is used as electrolyte, washed by clean water for several times, freeze-dried for 6h, and then vacuum-dried for 12h in a vacuum drying oven at 80 ℃ to obtain the carbon paper FEG treated by the electrochemical method.
2) Electrolyte BiCl3Preparation of the ethylene glycol solution of (1): weigh 0.3g of BiCl3Dissolving the mixture in 25mL of ethylene glycol, and magnetically stirring the mixture for 1h at room temperature to obtain electrolyte BiCl3The ethylene glycol solution of (1).
3)Bi2O3Preparation of @ FEG: FEG as working electrode, platinum sheet electrode as counter electrode and reference electrode, and BiCl3The ethylene glycol solution of (2) was used as an electrolyte at 1mA cm-2Carrying Bi on the obtained solid carrier by electrodeposition for 5min under constant current density2O3Taking out the carbon material substrate of the catalyst nano particles, washing with ethanol for several times, and drying in vacuumVacuum drying at 70 ℃ for 24h in a drying box to obtain the bismuth-based self-supporting electrocatalyst Bi2O3@FEG。
(II) detection results:
FIG. 1 shows Bi prepared in example 12O3SEM image of @ FEG. From FIG. 1, Bi can be seen2O3The nanoparticles are supported on the surface of FEG in a large amount and uniformly.
FIG. 2 shows Bi prepared in example 12O3The TEM image of @ FEG. From FIG. 2, the catalytically active substance Bi can be seen2O3The catalyst is uniformly distributed on the surface of FEG, and no obvious agglomeration occurs, thus being beneficial to electrocatalysis of nitrogen reduction to produce ammonia.
FIG. 3 shows Bi prepared in example 12O3The synthesis diagram of @ FEG. As can be seen from fig. 3, compared with the common carbon paper, the FEG has an increased interlayer spacing and an increased specific surface area, and facilitates the immobilization of the catalytically active material.
FIG. 7 shows Bi prepared in example 12O3The XRD pattern of @ FEG. From FIG. 7, we can see that Bi is successfully prepared2O3And successfully immobilized on the FEG.
Example 2 bismuth-based self-supporting electrocatalyst (Bi)2O3@ FEG) electrocatalytic nitrogen reduction to produce ammonia
The experimental method comprises the following steps: under the environmental condition, an H-type electrolytic cell is used as an electrolytic bath, and 0.1M Na is used2SO4The solution is used as electrolyte, the volume of the electrolyte is 70mL, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and Bi is added2O3The @ FEG clamp was placed on a platinum electrode clamp and used directly as the working electrode. And carrying out an electro-catalytic nitrogen reduction ammonia production experiment under the nitrogen atmosphere. After the experiment, Bi can be added2O3@ FEG was washed with ultrapure water several times, and washed with an electrolyte several times before the next use, and then used as it is.
The product was analyzed with an ammonia sensitive electrode. As shown in FIGS. 4 and 5, the highest ammonia production efficiency of the conversion of nitrogen into ammonia gas can reach 5.955 mugNH3h-1cm-2The highest Faraday efficiency can reach 11.472%. As shown in figure 6, the catalyst is repeatedly used for 5 times, and the catalytic ammonia production efficiency is not obviously reducedLow. The catalyst has ideal application prospect in the field of ammonia production by nitrogen reduction.
Claims (9)
1. The bismuth-based self-supporting electrocatalyst is characterized in that the bismuth-based self-supporting electrocatalyst is prepared by immobilizing Bi on a carbon material substrate treated by an electrochemical method2O3The bismuth-based self-supporting electrocatalyst is obtained by using the catalyst nanoparticles.
2. The bismuth-based self-supporting electrocatalyst according to claim 1, wherein the carbon material substrate is carbon paper.
3. A process for the preparation of a bismuth-based self-supporting electrocatalyst according to claim 2, characterized in that the process is as follows: performing electrodeposition with salt solution of bismuth as electrolyte under constant current density by using carbon paper treated by electrochemical method as working electrode, platinum sheet electrode as counter electrode and reference electrode, and the obtained immobilized Bi2O3Taking out the carbon material substrate of the catalyst nano-particles, washing with ethanol for a plurality of times, and drying in vacuum to obtain the bismuth-based self-supporting electrocatalyst Bi2O3@FEG。
4. The process for preparing a bismuth-based self-supporting electrocatalyst according to claim 3, characterized in that the electrodeposition current density is 1mA cm-2The time of electrodeposition is 5-10 min.
5. The method for preparing the bismuth-based self-supporting electrocatalyst according to claim 3, wherein the carbon paper treated by the electrochemical method is prepared by the following steps: the carbon paper is used as a working electrode, a calomel electrode is used as a reference electrode, the other piece of carbon paper is used as a counter electrode, the carbon paper is treated in a range of 0.6 to 1.8V by CV, soaked in deionized water for 12h, cleaned for a plurality of times by deionized water after passing through 8000 s and 10000s at i-t constant voltage, treated in a range of-1 to 0.9V by CV, cleaned for a plurality of times by clear water, freeze-dried for 6h, and then vacuum-dried for 12h in a vacuum drying box, so that the carbon paper FEG treated by the electrochemical method is obtained.
6. The method of claim 3, wherein the electrolyte is BiCl3A glycol solution of (a); the preparation method comprises the following steps: adding BiCl3Adding into ethylene glycol, stirring for 1h at room temperature to obtain BiCl3The ethylene glycol solution of (1).
7. The method of claim 6, wherein the BiCl is a bismuth-based self-supporting electrocatalyst3The concentration of the ethylene glycol solution is 0.2-0.5 mol.L-1。
8. Use of the bismuth-based self-supporting electrocatalyst according to claim 1 or 2 for electrocatalytic nitrogen reduction to ammonia.
9. Use according to claim 8, characterized in that the method is as follows: h-type electrolytic cell is used as electrolytic bath, Na is used2SO4The solution is used as an electrolyte and Bi2O3The @ FEG is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the ammonia is produced by electrocatalytic nitrogen reduction in a nitrogen atmosphere.
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| CN112481645A (en) * | 2020-10-22 | 2021-03-12 | 杭州师范大学 | Preparation method of silicon-based catalyst for nitrogen photoelectrochemical reduction |
| CN113073354A (en) * | 2021-03-25 | 2021-07-06 | 辽宁大学 | Bismuth and ruthenium bimetal self-supporting electrocatalytic material, preparation method thereof and application thereof in nitrogen reduction |
| CN113707891A (en) * | 2021-08-24 | 2021-11-26 | 辽宁大学 | Self-supporting electrode substrate material and double-chamber enzyme biofuel cell based on same |
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| CN114196984A (en) * | 2022-01-20 | 2022-03-18 | 辽宁大学 | Constant-current electrodeposited copper-based catalyst on carbon paper, preparation method thereof and application of catalyst in electrocatalysis of 4-ethynylaniline |
| CN114892200A (en) * | 2022-05-10 | 2022-08-12 | 江苏大学 | Preparation of carbon paper loaded Bi nano material by electrodeposition method and application thereof in electrocatalytic reduction of CO 2 |
| CN115624964A (en) * | 2022-10-13 | 2023-01-20 | 长沙学院 | Bi with fern-shaped hierarchical structure 2 O 3 Preparation method of-carbon paper flexible composite photocatalyst |
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