CN113506881B - Carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode and preparation process and application thereof - Google Patents
Carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode and preparation process and application thereof Download PDFInfo
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- CN113506881B CN113506881B CN202110787117.9A CN202110787117A CN113506881B CN 113506881 B CN113506881 B CN 113506881B CN 202110787117 A CN202110787117 A CN 202110787117A CN 113506881 B CN113506881 B CN 113506881B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 136
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 129
- 239000011777 magnesium Substances 0.000 title claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 65
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 63
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 56
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 5
- 229940091250 magnesium supplement Drugs 0.000 claims description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 6
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 102000020897 Formins Human genes 0.000 claims description 4
- 108091022623 Formins Proteins 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000002285 radioactive effect Effects 0.000 abstract description 4
- 230000000813 microbial effect Effects 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- -1 cerium ions Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002354 radioactive wastewater Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000863430 Shewanella Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- 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
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
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- 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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode and a preparation process and application thereof, belonging to the technical field of sewage purification and wastewater resource utilization. The preparation method comprises the following steps: 1. removing impurities attached to the carbon felt, drying, and etching the dried carbon felt; 2. taking the carbon felt pretreated in the step 1 as a raw material, and loading iron, magnesium and chitosan on the surface of the carbon felt obtained in the step 1 by a hydrothermal method; 3. taking the carbon felt-based iron/magnesium/nitrogen doped carbon catalytic electrode obtained in the step 2 as a raw material, and loading a zirconium metal organic framework structure on the surface of the carbon felt obtained in the step 2 through a hydrothermal method; the iron, magnesium and zirconium are then oxidized by calcination. The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode is applied to a Microbial Fuel Cell (MFC) and optimizes a treatment process, so that radioactive ions in nuclear wastewater are removed, and rare earth metals are recovered.
Description
Technical Field
The invention relates to a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode, a preparation process and application thereof,
Belongs to the technical field of sewage purification and wastewater resource utilization.
Background
Microbial Electrochemical Systems (MES) have become the most promising wastewater treatment methods as a green technology for treating wastewater using metabolic activities of electricity-producing microorganisms. As a widely used MES, microbial Fuel Cells (MFCs) consume organic matter through metabolic activity of anode-producing microorganisms, generate electrons and transfer to a cathode through an external circuit. In this process, the organic matter is degraded while generating electric energy. The traditional nuclear wastewater treatment method mainly comprises adsorption, membrane filtration and the like, and the research on treating the nuclear wastewater by adopting an electrochemical method is less.
In recent years, as an emerging green technology, research on MFC is rapidly advanced, electricity generation and wastewater performance are remarkably improved, and common problems of high internal resistance and low power in practical application are urgently solved. Wherein the efficiency of the MFC cathode reduction affects the rate of end electron acceptor and electron binding in the cathode compartment, severely limiting the overall performance of the MFC. Although many scholars have optimized the materials of the cathode, the problem has not been solved effectively. In order to improve the reduction efficiency of the cathode electron acceptor, the doping of the cathode surface with a transition metal catalyst has been receiving a great deal of attention.
The research on preparing the cathode of the polycrystalline catalyst with the carbon felt as a substrate and the iron/magnesium/zirconium composite oxide supported on the surface, improving the performance of the MFC and treating and recycling cobalt, strontium, cesium, lanthanum and cerium in the nuclear wastewater is still blank.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode and the preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The invention aims to provide a preparation process of a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode, which is characterized by comprising the following steps of:
(1) Pretreatment of carbon felt: removing impurities attached to the carbon felt, drying, and etching the dried carbon felt;
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode; taking the carbon felt pretreated in the step (1) as a raw material, and loading iron, magnesium and chitosan on the surface of the carbon felt obtained in the step (1) by a hydrothermal method;
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: taking the carbon felt-based iron/magnesium/nitrogen doped carbon catalytic electrode obtained in the step (2) as a raw material, and loading a zirconium metal organic framework structure on the surface of the carbon felt obtained in the step (2) through a hydrothermal method; the iron, magnesium and zirconium are then oxidized by calcination.
In the step (1), the specific steps of removing the impurities attached to the carbon felt are as follows: immersing the carbon felt in a mixed solution of absolute ethyl alcohol and acetone for 24-48 h, wherein the mass ratio of the absolute ethyl alcohol to the acetone is 1:2-2:1, drying at 60-100 ℃;
In the step (1), the specific steps of the etching treatment are as follows: immersing the dried carbon felt in dilute acid, etching 12-24 h and drying at 60-100 ℃ to generate adhesion sites of the catalyst;
In the step (2), the specific steps of loading iron, magnesium and chitosan on the surface of the carbon felt obtained in the step (1) by a hydrothermal method are as follows: firstly, chitosan is dissolved in dilute acid, and stirred for 12-24 h to form a viscous solution, ferric trichloride hexahydrate and magnesium chloride hexahydrate are added in the stirring process, and the mass ratio of the chitosan, the dilute acid, the ferric trichloride hexahydrate and the magnesium chloride hexahydrate is (18-20): (826-828): (2-4): (1-2); transferring the viscous solution into a reaction kettle, putting the carbon felt obtained in the step (1), performing hydrothermal treatment on the carbon felt in a baking oven at 180 ℃ for 12 h, and finally, cleaning the carbon felt by deionized water and drying the carbon felt at 60-100 ℃;
In the step (3), the specific steps of loading the zirconium metal organic framework structure on the surface of the carbon felt obtained in the step (2) by a hydrothermal method are as follows: firstly, dissolving zirconium tetrachloride and terephthalic acid in N, N-Dimethylformamide (DMF), wherein the mass ratio of the zirconium tetrachloride to the terephthalic acid to the DMF is (2-4): (1-2): (836-838); transferring the mixed solution to a reaction kettle of 50mL, putting the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2), and carrying out hydrothermal treatment on the carbon felt-based iron/magnesium/chitosan catalytic electrode in a baking oven at 120 ℃ for 24: 24 h; then, washing the carbon felt with absolute ethanol and DMF and drying at 60-100 ℃ to remove unreacted substances;
In the step (3), the specific steps of oxidizing iron, magnesium and zirconium by calcination are as follows: controlling the temperature rising rate to be 5 ℃ for min - 1, and calcining at 600 ℃ for 120 min;
The second purpose of the invention is to prepare the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode by adopting the preparation process.
The invention further aims to apply the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode to the treatment of nuclear wastewater, and the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode disclosed by the invention realizes the removal of cobalt, strontium, cesium, lanthanum and cerium ions and the recovery of rare earth metals in radioactive wastewater.
The beneficial effects of the invention are as follows:
The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode for reducing noble metal cobalt, strontium, cesium, lanthanum and cerium ions can remarkably improve the electrochemical performance of a cathode, further promote the accelerated metabolism of anode electrogenesis microorganisms and further improve the system voltage; meanwhile, the catalytic electrode is used as a reduction site of cobalt, strontium, cesium, lanthanum and cerium ions, so that radioactive ions can be effectively reduced, and efficient removal and recovery of the radioactive ions are realized; the catalytic electrode with the reduced metal simple substance loaded on the surface can be used as an anode, and released in an ion form in an anode chamber, so that the regenerability of the electrode is demonstrated; the MFC anode chamber takes the iron anode as a main anode, and the active carbon/graphite particle biological anode as an auxiliary anode, so that the specific surface area of the anode is increased, the adhesion of electrogenesis microorganisms is facilitated, and the performance of the MFC is improved.
Drawings
FIG. 1 is a cyclic voltammogram of a carbon-felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode of the difference between the reduction of radioactive ions of example 1 and comparative examples 1-3 (in the figure: the abscissa represents voltage, the unit V; the ordinate represents current, the unit A; fe (1)/Mg(1)/Zr@NC-CF-C corresponds to comparative example 1, fe (1)/Mg(2)/Zr@NC-CF-C corresponds to comparative example 2, fe (1)/Mg(2)/Zr@NC-CF-H corresponds to comparative example 3, fe (1)/Mg(1)/Zr@NC-CF-H corresponds to example 1);
FIG. 2 is a graph showing the treatment performance of carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrodes for treating cerium at various concentrations (in the graph, the abscissa represents time in h, the left side of the ordinate represents cerium ion concentration in mg L - 1, the right side represents removal efficiency in mg L - 1), and the right side of the graph indicates cerium concentration in wastewater.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon (Fe (1)/Mg(1)/Zr@NC-CF-H) catalytic electrode was prepared as follows:
(1) Pretreatment of carbon felt: immersing the carbon felt in absolute ethyl alcohol and acetone according to the volume ratio of 1: 48 h in the mixed solution with the proportion of 1 and drying at 60 ℃; the dried carbon mat was then immersed in a 10% acetic acid solution, etched 24 h and dried at 60 ℃.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: firstly, 2 g chitosan is weighed and dissolved in 10 percent of acetic acid solution of 80 mL, and stirred for 24 h to form a viscous solution, wherein the molar ratio of iron to magnesium is 1:1 (1 mM:1 mM) ferric chloride hexahydrate and magnesium chloride hexahydrate; then transferring the viscous solution into a 100 mL reaction kettle, putting the carbon felt obtained in the step (1), and carrying out hydrothermal treatment on the carbon felt in a 180 ℃ oven for 12 h; finally, the carbon felt was rinsed with deionized water and dried at 60 ℃.
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: firstly, weighing the following components in a molar ratio of 1:1 (0.68 mM:0.68 mM) zirconium tetrachloride and terephthalic acid in 50 mL N, N-Dimethylformamide (DMF); transferring the mixed solution to a reaction kettle of 50 mL, putting the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2), and carrying out hydrothermal treatment on the carbon felt-based iron/magnesium/chitosan catalytic electrode in a baking oven at 120 ℃ for 24: 24 h; then, the carbon felt was washed with absolute ethanol and DMF and dried at 60 ℃ to remove unreacted materials; finally, the dried catalytic electrode was calcined at 600 ℃ for 120 min (a rate of temperature rise of 5 ℃ for min - 1, heat preservation of 120 min), thereby oxidizing the loaded iron, magnesium and zirconium on the electrode surface.
Comparative example 1
The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon (Fe (1)/Mg(1)/Zr@NC-CF-C) catalytic electrode was prepared as follows:
(1) Pretreatment of carbon felt: as in example 1.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: as in example 1.
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: first, the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2) is calcined at 600 ℃ for 120 min (the temperature rising rate is 5 ℃ for min - 1, and the temperature is kept for 120 min), so that the loaded iron and magnesium on the surface of the electrode are oxidized. Then, the molar ratio was weighed to be 1:1 in 50mL N, N-Dimethylformamide (DMF); then, transferring the mixed solution into a reaction kettle of 50mL, placing the mixed solution into a calcined catalytic electrode, and carrying out hydrothermal treatment on the mixed solution in a baking oven at 120 ℃ for 24: 24 h; finally, the carbon felt was washed with absolute ethanol and DMF and dried at 60 ℃ to remove unreacted materials.
Comparative example 2
The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon (Fe (1)/Mg(2)/Zr@NC-CF-C) catalytic electrode was prepared as follows:
(1) Pretreatment of carbon felt: as in example 1.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: referring to example 1, the difference from example 1 is that iron and magnesium are added during stirring in a molar ratio of 1:2 (1 mM:2 mM) of ferric chloride hexahydrate and magnesium chloride hexahydrate.
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: as in comparative example 1.
Comparative example 3
The carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon (Fe (1)/Mg(2)/Zr@NC-CF-H) catalytic electrode was prepared as follows:
(1) Pretreatment of carbon felt: as in example 1.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: as in comparative example 2.
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: as in example 1.
Test 1
The catalytic electrodes obtained in example 1 and comparative examples 1 to 3 were examined for redox properties.
Catalytic electrodes were tested for redox by cyclic voltammetry at a scan rate of 0.01V/s and cyclic voltammetry characterization of catalytic electrodes containing different catalysts in 1 mol L - 1 sodium sulfate solution, respectively, as shown in figure 1. As can be seen from fig. 1, the cyclic voltammogram has a distinct redox peak, indicating that the catalyst has a distinct promoting effect on the redox reaction of the electrode.
Test 2
The performance of the Fe (1)/Mg(1)/Zr@NC-CF-H catalytic electrode obtained in example 1 in treating radioactive wastewater was examined.
The structure of a dual-chamber MFC is mainly composed of an anode chamber, a cathode chamber, and a Proton Exchange Membrane (PEM) separating the two pole chambers. The double-chamber MFC takes an iron anode as a main anode, takes graphite particles and activated carbon particles (mass ratio is 1:1) inoculated with Shewanella electrogenerated as auxiliary anodes, and forms a composite anode of the MFC, and takes a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode Fe (1)/Mg(1)/Zr@NC-CF-H as an MFC cathode, and connects the anode and the cathode through a titanium wire, and simultaneously is externally connected with a resistor to form a complete loop. After the system is assembled, 100 mg L - 1 COD simulated wastewater is prepared and added into an anode chamber to provide organic matters required by self metabolism of electrogenic microorganisms. Solutions containing 1 g L - 1 cobalt, strontium, cesium, lanthanum and cerium ions were prepared as nuclear wastewater, diluted to different concentrations (5 mg L - 1、10 mg L- 1、20 mg L- 1 respectively) and added into a cathode chamber, and the performance of the system for treating cerium ions was tested, and the results are shown in fig. 2. Therefore, the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode can effectively reduce cerium ions, and basically realizes complete removal of cerium.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The preparation process of the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode is characterized by comprising the following steps of:
(1) Pretreatment of carbon felt: removing impurities attached to the carbon felt, drying, and etching the dried carbon felt;
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode; taking the carbon felt pretreated in the step (1) as a raw material, and loading iron, magnesium and chitosan on the surface of the carbon felt obtained in the step (1) by a hydrothermal method;
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode: taking the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2) as a raw material, and loading a zirconium metal organic framework structure on the surface of the carbon felt obtained in the step (2) through a hydrothermal method; then, iron, magnesium and zirconium are oxidized by calcination;
in the step (3), the specific steps of loading the zirconium metal organic framework structure on the surface of the carbon felt obtained in the step (2) by a hydrothermal method are as follows: firstly, dissolving zirconium tetrachloride and terephthalic acid in N, N-dimethylformamide, wherein the mass ratio of the zirconium tetrachloride to the terephthalic acid to the N, N-dimethylformamide is (2-4): (1-2): (836-838); transferring the mixed solution into a reaction kettle, putting the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2), and carrying out hydrothermal treatment on the carbon felt-based iron/magnesium/chitosan catalytic electrode in a baking oven at 120 ℃ for 24 h; then, washing the carbon felt with absolute ethanol and DMF and drying at 60-100 ℃ to remove unreacted substances;
The preparation process of the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode is characterized in that in the step (2), the hydrothermal method loads iron, magnesium and chitosan on the surface of the carbon felt obtained in the step (1) in the concrete steps of: firstly, chitosan is dissolved in dilute acid, and stirred for 12-24 h to form a viscous solution, ferric trichloride hexahydrate and magnesium chloride hexahydrate are added in the stirring process, and the mass ratio of the chitosan, the dilute acid, the ferric trichloride hexahydrate and the magnesium chloride hexahydrate is (18-20): (826-828): (2-4): (1-2); then transferring the viscous solution into a reaction kettle, putting the carbon felt obtained in the step (1), performing hydrothermal treatment on the carbon felt in a baking oven at 180 ℃ for 12h, and finally, cleaning the carbon felt by deionized water and drying the carbon felt at 60-100 ℃.
2. The process for preparing the carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode according to claim 1, wherein in the step (1), the specific steps of removing impurities attached to the carbon felt are as follows: immersing the carbon felt in a mixed solution of absolute ethyl alcohol and acetone for 24-48 h, wherein the mass ratio of the absolute ethyl alcohol to the acetone is 1:2-2:1, drying at 60-100deg.C.
3. The process for preparing a carbon felt based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode according to claim 1, wherein in step (1), the specific steps of the etching treatment are as follows: the dried carbon mat is immersed in dilute acid, etched 12-24 h and dried at 60-100 ℃ to create catalyst attachment sites.
4. A process for the preparation of carbon-felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrodes according to claim 1, characterized in that in step (3), the specific steps of oxidizing iron, magnesium and zirconium by calcination are: the temperature rising rate is controlled to be 5 ℃ for min - 1, and the calcination is performed at 600 ℃ for 120 min.
5. A carbon felt based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode prepared by the process of any one of claims 1-4.
6. The use of a carbon-felt based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode in accordance with claim 5 for treating nuclear wastewater.
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