LU501767B1 - Stainless steel-based mixed crystal catalytic electrode and preparation method thereof - Google Patents
Stainless steel-based mixed crystal catalytic electrode and preparation method thereof Download PDFInfo
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- LU501767B1 LU501767B1 LU501767A LU501767A LU501767B1 LU 501767 B1 LU501767 B1 LU 501767B1 LU 501767 A LU501767 A LU 501767A LU 501767 A LU501767 A LU 501767A LU 501767 B1 LU501767 B1 LU 501767B1
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- stainless steel
- cobalt
- catalytic electrode
- molybdenum
- steel mesh
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 41
- 239000010935 stainless steel Substances 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000013078 crystal Substances 0.000 title claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 36
- 239000010941 cobalt Substances 0.000 claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 229910017309 Mo—Mn Inorganic materials 0.000 claims abstract description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002135 nanosheet Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011883 electrode binding agent Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- -1 silver ions Chemical class 0.000 abstract description 8
- 230000005611 electricity Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000004060 metabolic process Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000007269 microbial metabolism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
- H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a stainless steel-based mixed crystal catalytic electrode and a manufacturing method thereof. The stainless steel mesh is used as a substrate, and oxides of cobalt, molybdenum and manganese are used as polycrystalline catalysts. The invention also discloses the preparation method of the cobalt-based molybdenum manganese catalytic electrode and the application of the cobalt-based molybdenum manganese catalytic electrode in the treatment of silver-containing wastewater. According to the invention, the cobalt-based Mo-Mn catalytic electrode for reducing noble metal silver is prepared, which can significantly improve the electrochemical performance of MFC, further promote the accelerated metabolism of anode electricity-producing microorganisms, and further improve the system voltage; at the same time, catalytic electrode, as the reduction site of precious silver, can effectively reduce silver ions and realize efficient removal and recovery of silver ions.
Description
DESCRIPTION LU501767 STAINLESS STEEL-BASED MIXED CRYSTAL CATALYTIC ELECTRODE AND
TECHNICAL FIELD The invention belongs to the technical field of sewage purification and wastewater resource utilization, and particularly relates to a stainless steel-based mixed crystal catalytic electrode and preparation method thereof.
BACKGROUND As a green technology to treat heavy metal wastewater by microbial metabolism, microbial electrochemical system (MES) has become the most promising wastewater treatment method. Compared with traditional fuel cells, microbial fuel cells (MFC) use microbial metabolism to consume organic matter and transfer the generated electrons to the cathode. In this process, not only organic matter is degraded, but also electricity is generated. At present, many scholars have proved that MFCs can also biodegrade heavy metal wastewater. Because of its high standard reduction potential, silver can be used as a potential terminal electron acceptor.
Although MFC, as a promising technology, has made great progress and its performance has been greatly improved, its shortcomings of high internal resistance and low power still need to be solved due to structural constraints. The redox efficiency of MFC cathode will affect the binding rate of terminal electron acceptor and electron in cathode chamber, which severely limits the overall performance of MFC. Although many scholars have optimized the performance and structure of MFC, these problems still severely limit the application of the system. In order to improve the cathode efficiency, doping different metal catalysts has become the best method. At present, it is still blank to use stainless steel mesh as substrate to compound molybdenum, manganese and cobalt oxides and compound oxide polycrystalline catalysts to improve MFC performance and to treat and recover silver in wastewater.
SUMMARY Aiming at the shortcomings of the prior art, the invention provides a stainless steel-based mixed crystal catalytic electrode and preparation method thereof. The cobalt-based Mo-Mn catalytic electrode of the invention realizes the complete removal of silver ions in silver-containing wastewater and basically realizes the complete recovery of silver by reasonabliJ501767 using the catalyst and optimizing the treatment process.
The specific technical scheme is as follows: One of the aims of the present invention is to provide a cobalt-based Mo-Mn catalytic electrode, which takes stainless steel mesh as the substrate; oxides of cobalt, molybdenum and manganese are used as polycrystalline catalysts.
Wherein, the oxide can include a single oxide of cobalt, molybdenum and manganese, or a composite oxide formed by any two or more elements of cobalt, molybdenum and manganese.
Furthermore, PVP (polyvinylpyrrolidone) is used as the electrode binder.
The second object of the present invention is to provide the preparation method of the cobalt-based molybdenum manganese catalytic electrode, which comprises the following steps: (1) preparing cobalt-based stainless steel mesh (Co-SS): attaching cobalt to the surface of stainless steel mesh by electrodeposition; then, obtaining a cobalt oxide-based stainless steel catalyst electrode by calcination; (2) preparing molybdenum manganese composite nanosheets; (3) preparing Co-based Mo-Mn catalytic electrode (Mo/Mn/Co-SS): using the Mo-Mn composite nanosheet obtained in step (2) as raw material, carrying Mo and Mn on the surface of the prepared Co-based stainless steel mesh obtained in step (1) through electrostatic spinning; then, oxidizing molybdenum and manganese by calcination.
Further, the specific working conditions of step (1) are: Adding boric acid and sodium dodecyl sulfate into the aqueous solution containing cobalt sulfate and cobalt chloride as electrolyte; carrying out electrodeposition with stainless steel mesh as anode and platinum sheet as counter electrode; then, calcining the electrodeposited stainless steel mesh to obtain the cobalt oxide-based stainless steel catalyst electrode.
Furthermore, in step (1), the calcination condition of stainless steel mesh is 650-750°C for 100-150 min. The heating rate is preferably 5 C/min.
Furthermore, in step (1), the saturated calomel electrode is used as the reference electrode, and the current is constantly applied to the electrochemical workstation for electrodeposition. The current is preferably 13 mAcm 2, and the electrodeposition time is preferably 30 min.
Furthermore, in step (1), in the aqueous solution containing cobalt sulfate and cobdlt)501767 chloride, the concentration of cobalt sulfate is 0.15-0.25 mol/L and the concentration of cobalt chloride is 0.08-0.12 mol/L.
Furthermore, in step (1), the dosage ratio of boric acid, sodium dodecyl sulfate and aqueous solution containing cobalt sulfate and cobalt chloride is (12-18) g:(10-15) g:1 L.
Further, the specific working conditions of step (2) are: Uniformly mixing manganese acetylacetonate, molybdenum hexacarbonyl, ascorbic acid and oleylamine; then, adding DMF (N,N-dimethylformamide) and introducing nitrogen continuously to remove oxygen in the solution; heating at 60-80 °C for 10-14 h; after centrifugation, obtaining the molybdenum-manganese composite nanosheet.
Furthermore, in step (2), the mass ratio of manganese acetylacetonate, molybdenum hexacarbonyl and ascorbic acid is (40-45):(56-65):630.
Furthermore, in step (2), the washing is washing with ethanol.
Further, the specific working conditions of step (3) are: Uniformly dispersing the molybdenum-manganese composite nanosheets obtained in step (2) in absolute ethanol to obtain Mo-Mn ethanol dispersion; dissolving polyvinylpyrrolidone in Mo-Mn ethanol dispersion, and loading the dispersion on the surface of cobalt-based stainless steel mesh obtained in step (1) by electrostatic spinning; then, calcining the cobalt-based stainless steel mesh in situ to carbonize polyvinylpyrrolidone, and oxidizing molybdenum and manganese elements to form variable valence metal oxides, and embedding in the surface of the cobalt-based stainless steel mesh.
Furthermore, in step (3), the operation of electrospinning is as follows: putting the solution into a plastic syringe with a stainless steel nozzle; at the same time, fixing the previously prepared Co-SS on the rotating drum to rotate it; putting the injector into the electrospinning device, connecting the positive lead from the high voltage power supply to the metal nozzle, and applying a high voltage of about 16 kV, which is fed by the injector pump.
Furthermore, in step (3), the calcination condition is 480-550°C for 100-150 min. The heating rate is preferably 5°C/min.
Furthermore, in step (3), the mass fraction of polyvinylpyrrolidone in the dispersion is 25wt%-40wt%.
Furthermore, in step (3), the dosage ratio of molybdenum-manganese composite nanosheet$/501 767 to absolute ethanol is (0.08-0.15) g:10 ml.
A third object of the present invention is to provide the application of the cobalt-based Mo-Mn catalytic electrode in the treatment of silver-containing wastewater. The cobalt-based molybdenum manganese catalytic electrode of the invention realizes the complete removal of silver ions in silver-containing wastewater and basically realizes the complete recovery of silver. At the same time, catalytic electrode, as the reduction site of precious silver, can effectively reduce silver ions and realize efficient removal and recovery of silver ions. The reduced silver ions on the electrode surface can further promote the electrochemical performance of the system, increase the system voltage and further improve the capacity of the system to treat wastewater. The micro-electric field generated by iron anode and graphite bio-anode in MFC chamber can promote the high-speed growth of electricity-producing microorganisms and increase the removal efficiency of organic pollutants.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is the cyclic voltammograms of different catalytic electrodes obtained in Example 1 and Comparative Examples 1-3 (in the figure, the abscissa represents the voltage in v; the ordinate represents the current in A; Co-SS corresponding comparative example 1, Mn/Co-SS corresponding comparative example 2, Mo/Co-SS corresponding comparative example 3 and Mo/Mn/Co-SS corresponding example 1); Fig. 2 shows the treatment performance of cobalt-based Mo-Mn catalytic electrode for reducing noble metal silver in treating wastewater containing Ag’ with different concentrations (in the figure: the abscissa indicates time in h; the left ordinate represents the effluent concentration and the right represents the removal efficiency; the note on the right represents the concentration of silver in wastewater in mg/L).
DESCRIPTION OF THE INVENTION The principles and features of the present invention are described below with examples, which are only used to explain the present invention, not to limit its scope.
In a specific embodiment, the ethanol is absolute ethanol.
Example 1 The preparation of cobalt-based Mo-Mn catalytic electrode comprises the following steps:
(1) preparing cobalt-based stainless steel mesh: putting 15 g boric acid and 12 g sodiuhV501767 dodecyl sulfate into 1 L of aqueous solution containing 0.2 mol cobalt sulfate and 0.1 mol cobalt chloride; then, stirring the mixed solution at room temperature for 2 hours; then, using the mixed solution as electrolyte, stainless steel mesh as anode, platinum sheet as counter electrode, saturated calomel electrode as reference electrode, applying a constant current of 13 mAcm-2 on electrochemical workstation for electrodeposition for 30 min; then, calcining the electrodeposited stainless steel mesh at 700°C for 2 h (the heating rate is 5 ‘C/min, and the temperature is kept for 120 min); finally, obtaining the cobalt tetroxide-based stainless steel catalyst electrode by cooling at room temperature, which is labeled as Co-SS.
(2) preparing Mo-Mn composite nanosheets: uniformly mixing 41.55 mg of manganese acetylacetonate, 60.00 mg of molybdenum hexacarbonyl, 630.00 mg of ascorbic acid and 40.00 mL of oleylamine; then, adding 7.50 mL DMF and introducing nitrogen continuously for 30 min to remove oxygen in the solution; then heating at 80°C for 12 h; washing the precipitate obtained after centrifugation with ethanol, and finally, obtaining molybdenum-manganese composite nanosheets.
(3) preparing Co-based Mo-Mn catalytic electrode: dispersing 0.1 g of Mo-Mn composite nanosheets obtained in step (2) in 10 mL of anhydrous ethanol at room temperature to obtain Mo-Mn ethanol dispersion; dissolving PVP powder in Mo-Mn ethanol dispersion liquid system and mechanically stirring for 2 h; the weight fraction of PVP in the dispersion is 30wt%; then putting the above solution into a 10 mL plastic syringe with 20 G stainless steel nozzle; meanwhile, fixing the previously prepared Co-SS on a rotating drum with a diameter of 10 cm and rotating at a speed of 500 rpm; putting the injector into the electrospinning device, connecting the positive lead from the high-voltage power supply to the metal nozzle, and applying a high voltage of 16 kV (the negative pressure of the system is set to -2 kV), which is fed by the injector pump at a flow rate of 0.5 mL/h; then, treating the electrospun catalytic electrode in a tube furnace at 500°C for 120 min (heating rate is 5°C/min, holding time is 120 min) to carbonize PVP; at the same time, during the treatment, oxidizing Mo-Mn element to form variable valence metal oxide and embedding in the surface of catalytic electrode, and marking the product as Mo/Mn/Co-SS.
Comparative example 1
Co-SS is prepared according to the method of step (1) in Example 1. LU501767 Comparative example 2 The preparation of cobalt-based manganese catalytic electrode comprises the following steps: (1) preparing cobalt-based stainless steel mesh: same as Example 1.
(2) preparing manganese nanosheets: uniformly mixing 41.55 mg of manganese acetylacetonate, 630.00 mg of ascorbic acid and 40.00 mL of oleylamine; then, adding 7.50 mL DMF and continuously introducing nitrogen for 30 min to remove oxygen in the solution; then, heating at 80°C for 12 h; washing the precipitate obtained after centrifugation with ethanol, and finally, obtaining manganese nanosheets.
(3) preparing cobalt-based manganese catalytic electrode: refer to Example 1, which is different from Example 1 in that replacing the same mass of molybdenum-manganese composite nanosheets by manganese nanosheets obtained in step (2); marking the product as Mn/Co-SS.
Comparative example 3 The preparation of cobalt-based manganese catalytic electrode comprises the following steps: (1) preparing cobalt-based stainless steel mesh: same as Example 1.
(2) preparing molybdenum nanosheets: evenly mixing 60.00 mg of molybdenum hexacarbonyl, 630.00 mg of ascorbic acid and 40.00 mL of oleylamine; then, adding 7.50 mL DMF and continuously introducing nitrogen for 30 min to remove oxygen in the solution; then, heating at 80°C for 12 h; washing the precipitate obtained after centrifugation with ethanol, and finally, obtaining molybdenum nanosheets.
(3) preparing cobalt-based molybdenum catalytic electrode: refer to Example 1, which is different from Example 1 in that replacing the same mass of molybdenum-manganese composite nanosheets by molybdenum nanosheets obtained in step (2); marking the product as Mo/Co-SS.
Test 1 The catalytic electrodes obtained in Example 1 and Comparative Examples 1-3 are examined for redox.
The oxidation-reduction test of catalytic electrode is carried out by cyclic voltammetry at a scanning speed of 0.01 V/s. The catalytic electrodes containing different catalysts are characterized by cyclic voltammetry in 98% concentrated sulfuric acid solution, and the result$/501 767 are shown in Figure 1. As can be seen from Figure 1, the cyclic voltammetric curve has obvious redox peak, which shows that the catalyst can obviously promote the redox reaction of the electrode.
Test 2 The Mo/Mn/Co-SS obtained in example 1 is tested for its performance in treating silver-containing wastewater.
Co-based Mo-Mn catalytic electrode Mo/Mn/Co-SS is used as cathode of BEMFC, iron sheet is used as anode electrode, graphite particles and activated carbon particles (mass ratio 1:1) are completely filled in anode chamber as bio-anode, and electricity-producing Shiva is inoculated in anode chamber. After the electricity generation of the equipment is stable, the simulated wastewater of 400 ppm COD is prepared to enter the water from the anode to provide the organic matter metabolized by the electricity-producing microorganisms themselves. At the same time, AgSO4 solutions with different concentrations are prepared as silver-containing wastewater (the concentrations were 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L and 300 mg/L respectively), which are directly connected to the cathode, and the performance of the system in treating silver-containing wastewater was tested. The results are shown in Figure 2. It can be seen that the cobalt-based Mo-Mn catalytic electrode of the invention can effectively reduce silver ions and basically realize the complete recovery of silver.
The above description is only the preferred embodiment of the present invention, and it is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention.
Claims (9)
1. À stainless steel-based mixed crystal catalytic electrode, characterized in that a stainless steel mesh is used as a substrate; oxides of cobalt, molybdenum and manganese are used as polycrystalline catalysts.
2. The stainless steel-based mixed crystal catalytic electrode according to claim 1, characterized in that polyvinylpyrrolidone is used as the electrode binder.
3. A preparation method of stainless steel-based mixed crystal catalytic electrode, characterized by comprising the following steps: (1) preparing a cobalt-based stainless steel mesh: cobalt adheres to the surface of the stainless steel mesh by electrodeposition; then, obtaining cobalt oxide-based stainless steel catalytic electrode by in-situ calcination; (2) preparing molybdenum manganese composite nanosheets; (3) preparing cobalt-based Mo-Mn catalytic electrode: using the Mo-Mn composite nanosheets obtained in step (2) as raw materials, carrying Mo and Mn on the surface of the Co-based stainless steel mesh prepared in step (1) through electrostatic spinning; then, oxidizing molybdenum and manganese by calcination.
4. The preparation method according to claim 3, characterized in that the specific working conditions in step (3) are: uniformly dispersing the molybdenum-manganese composite nanosheets obtained in step (2) in absolute ethanol to obtain a Mo-Mn ethanol dispersion liquid; dissolving polyvinylpyrrolidone in Mo-Mn ethanol dispersion liquid, and loading the dispersion liquid on the surface of cobalt-based stainless steel mesh obtained in step (1) by electrostatic spinning; then, calcining the cobalt-based stainless steel mesh in situ to carbonize polyvinylpyrrolidone, oxidizing molybdenum and manganese elements and embedding into the surface of the cobalt-based stainless steel mesh.
5. The preparation method according to claim 4, characterized in that in step (3), the calcination condition is 480-550°C for 100-150 min.
6. The preparation method according to claim 3, characterized in that the working conditions of step (1) are:
adding boric acid and sodium dodecyl sulfate into the aqueous solution containing cobdlV501767 sulfate and cobalt chloride as electrolyte; carrying out electrodeposition with stainless steel mesh as anode and platinum sheet as counter electrode; then, calcining the electrodeposited stainless steel mesh in situ to obtain the cobalt oxide-based stainless steel catalytic electrode.
7. The preparation method according to claim 6, characterized in that in step (1), the calcination condition of stainless steel mesh is 650-750°C for 100-150 min.
8. The preparation method according to claim 3, characterized in that the working conditions of step (2) are: uniformly mixing manganese acetylacetonate, molybdenum hexacarbonyl, ascorbic acid and oleylamine; then, adding N,N-dimethylformamide and continuously introducing nitrogen; heating at 60-80°C for 10-14 h; after centrifugation, obtaining the molybdenum-manganese composite nanosheet.
9. An application of the cobalt-based Mo-Mn catalytic electrode according to claim 1 or 2 in treating silver-containing wastewater.
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