CN113506881A - 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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- CN113506881A CN113506881A CN202110787117.9A CN202110787117A CN113506881A CN 113506881 A CN113506881 A CN 113506881A CN 202110787117 A CN202110787117 A CN 202110787117A CN 113506881 A CN113506881 A CN 113506881A
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- zirconium
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 126
- 239000011777 magnesium Substances 0.000 title claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 62
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 59
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 21
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 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 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 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
- 230000008569 process Effects 0.000 claims abstract description 4
- 229940091250 magnesium supplement Drugs 0.000 claims description 53
- 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 12
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 239000002253 acid 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
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 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
- 238000011084 recovery Methods 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 8
- 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
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- 239000002131 composite material Substances 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
- 239000002354 radioactive wastewater Substances 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
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 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
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 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
- 238000001075 voltammogram Methods 0.000 description 1
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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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- 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
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- H01M4/8825—Methods for deposition of the catalytic active composition
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- 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
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- 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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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 metal organic framework structure of zirconium on the surface of the carbon felt obtained in the step 2 by a hydrothermal method; then, iron, magnesium and zirconium were 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 the treatment process, so that the removal of radioactive ions in nuclear wastewater and the recovery of rare earth metals are realized.
Description
Technical Field
The invention relates to a carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode and a preparation process and application thereof,
belongs to the technical field of sewage purification and wastewater resource utilization.
Background
The Microbial Electrochemical System (MES) has become the most promising wastewater treatment method as a green technology for treating wastewater by utilizing the metabolic activity of electrogenic microorganisms. As a widely used MES, Microbial Fuel Cells (MFCs) consume organic substances by the metabolic activity of anode-producing microorganisms, generate electrons, and transfer them to a cathode through an external circuit. In this process, the organic matter is degraded while generating electric power. Recently, the fact that the nuclear waste water is discharged into the sea in Japan has attracted considerable attention. 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 a new green technology, research on MFC has been advanced rapidly, and the improvement of electricity generation and wastewater performance is remarkable, and the common problems of high internal resistance and low power in practical application thereof need to be solved urgently. Where the cathode reduction efficiency of the MFC affects the rate of binding of the terminal electron acceptor and electrons in the cathode compartment, severely limiting the overall performance of the MFC. Although many scholars have optimized the cathode material, surface catalyst, the problem has not been solved effectively. In order to improve the reduction efficiency of the cathode electron acceptor, doping the surface of the cathode with a transition metal catalyst has received much attention.
The research on the aspects of preparing the cathode of the polycrystalline catalyst which takes the carbon felt as the substrate and loads the iron/magnesium/zirconium composite oxide on the surface, improving the performance of the MFC and treating and recovering 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 provides the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode and the preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the purposes of the invention is 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:
(1) pretreatment of the 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 metal organic framework structure of zirconium on the surface of the carbon felt obtained in the step (2) by a hydrothermal method; then, iron, magnesium and zirconium were oxidized by calcination.
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 60-100 ℃;
in the step (1), the etching treatment specifically comprises the following steps: immersing the dried carbon felt in dilute acid, etching for 12-24 h and drying at 60-100 ℃ to generate attachment sites of the catalyst;
in the step (2), the hydrothermal method for loading iron, magnesium and chitosan on the surface of the carbon felt obtained in the step (1) comprises the following specific steps: firstly, dissolving chitosan in dilute acid, stirring for 12-24 h to form viscous solution, adding ferric trichloride hexahydrate and magnesium chloride hexahydrate in the stirring process, wherein 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 for 12 hours in a drying oven at 180 ℃, and finally, cleaning the carbon felt with deionized water and drying at 60-100 ℃;
in the step (3), the step of loading the metal-organic framework structure of zirconium on the surface of the carbon felt obtained in the step (2) by a hydrothermal method comprises the following specific steps: 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); then, transferring the mixed solution into a 50 mL reaction kettle, putting the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2), and carrying out hydrothermal treatment in a 120 ℃ oven for 24 hours; then, washing the carbon felt with absolute ethyl alcohol and DMF and drying at 60-100 ℃ to remove unreacted substances;
in the step (3), the step of oxidizing iron, magnesium and zirconium by calcination comprises the following specific steps: controlling the heating rate to be 5 ℃ for min - 1Calcining at 600 deg.C for 120 min;
the invention also aims to provide the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode prepared by the preparation process.
The carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode realizes the removal of cobalt, strontium, cesium, lanthanum and cerium ions in radioactive wastewater and the recovery of rare earth metals.
The invention has the following beneficial effects:
the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode for reducing noble metal cobalt, strontium, cesium, lanthanum and cerium ions is prepared, the electrochemical performance of the cathode can be obviously improved, the accelerated metabolism of the anode electrogenesis microorganisms is promoted, and the system voltage is further improved; 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 the radioactive ions can be efficiently removed and recovered; the catalytic electrode with the reduced metal simple substance loaded on the surface can be used as an anode and released in an anode chamber in an ion form, so that the electrode has the regenerability; the MFC anode chamber takes the iron anode as a main anode and the activated carbon/graphite particle biological anode as an auxiliary anode, so that the specific surface area of the anode is increased, the attachment of electrogenic microorganisms is facilitated, and the performance of the MFC is improved.
Drawings
FIG. 1 shows example 1Cyclic voltammograms of different reduced radioactive ion carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrodes than those of comparative examples 1-3 (in the figures: abscissa represents voltage in V; ordinate represents current in 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 performance of a carbon felt-based Fe/Mg/Zr/N doped carbon catalytic electrode in treating cerium ions of different concentrations (in the graph, the abscissa represents time in h; and the left side of the ordinate represents the concentration of cerium ions in mg L) - 1The right side represents the removal efficiency in%; the right annotation of the graph represents the concentration of cerium in the wastewater in mg L - 1）。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon (Fe)(1)/Mg(1)The method comprises the following steps of:
(1) pretreatment of the carbon felt: immersing the carbon felt in absolute ethyl alcohol and acetone according to a volume ratio of 1: 1, drying the mixture for 48 hours at 60 ℃; the dried carbon felt was then immersed in a 10% acetic acid solution, etched for 24 h and dried at 60 ℃.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: firstly, weighing 2 g of chitosan, dissolving the chitosan in 10 percent of 80 mL of acetic acid solution, stirring for 24 hours to form viscous solution, and adding a mixture of iron and magnesium with the molar ratio of 1: 1 (1 mM: 1 mM) of 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 in a 180 ℃ oven for 12 hours; 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 a mixture of 1: 1 (0.68 mM: 0.68 mM) of zirconium tetrachloride and terephthalic acid, dissolved in 50 mL of N, N-Dimethylformamide (DMF); then, transferring the mixed solution into a 50 mL reaction kettle, putting the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2), and carrying out hydrothermal treatment in a 120 ℃ oven for 24 hours; then, the carbon felt was washed with absolute ethanol and DMF and dried at 60 ℃ to remove unreacted substances; finally, the dried catalytic electrode was calcined at 600 ℃ for 120 min (rate of temperature rise 5 ℃ C. min.) - 1And keeping the temperature for 120 min), thereby oxidizing the iron, magnesium and zirconium loaded on the surface of the electrode.
Comparative example 1
Preparation of carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon (Fe)(1)/Mg(1)The method comprises the following steps of:
(1) pretreatment of the carbon felt: the same as in example 1.
(2) Preparing a carbon felt-based iron/magnesium/chitosan catalytic electrode: the same as in example 1.
(3) Preparing a carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode: firstly, calcining the carbon felt-based iron/magnesium/chitosan catalytic electrode obtained in the step (2) at 600 ℃ for 120 min (the heating rate is 5 ℃ for min - 1And keeping the temperature for 120 min), thereby oxidizing the iron and magnesium loaded on the surface of the electrode. Then, weighing the mixture with a molar ratio of 1: 1, in 50 mL of N, N-Dimethylformamide (DMF); then transferring the mixed solution into a 50 mL reaction kettle, putting the calcined catalytic electrode into the reaction kettle, and carrying out hydrothermal treatment in a 120 ℃ oven for 24 hours; finally, the carbon felt was washed with absolute ethanol and DMF and dried at 60 ℃ to remove unreacted materials.
Comparative example 2
Preparation of carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon (Fe)(1)/Mg(2)/Zr@ NC-CF-C) catalytic electrode, the procedure is as follows:
(1) pretreatment of the carbon felt: the same 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 were added 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
Preparation of carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon (Fe)(1)/Mg(2)The method comprises the following steps of:
(1) pretreatment of the carbon felt: the same 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: the same as in example 1.
The redox properties of the catalytic electrodes obtained in example 1 and comparative examples 1 to 3 were examined.
The oxidation-reduction test of the catalytic electrode is carried out by adopting cyclic voltammetry, the scanning speed is 0.01V/s and is 1 mol L- 1The catalytic electrodes containing different catalysts were subjected to cyclic voltammetry characterization in sodium sulfate solution, and the results are shown in fig. 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
For Fe obtained in example 1(1)/Mg(1)And the performance test of treating the radioactive wastewater is carried out by the/Zr @ NC-CF-H catalytic electrode.
The structure of the double-chamber MFC mainly comprises an anode chamber, a cathode chamber and a Proton Exchange Membrane (PEM) separating the two electrode chambers. The double-chamber MFC takes an iron anode as a main anode, takes graphite particles inoculated with Shewanella oxytoca and activated carbon particles (the mass ratio is 1: 1) as an auxiliary anode, the two form a composite anode of the MFC, and the carbon felt is based on iron/magnesiumZirconium/nitrogen doped carbon catalytic electrode Fe(1)/Mg(1)the/Zr @ NC-CF-H is used as an MFC cathode, is connected with an anode and a cathode through a titanium wire, and is externally connected with a resistor to form a complete loop. After the system was assembled, 100 mg L of the solution was prepared - 1COD simulating waste water is added into the anode chamber to provide organic matters required by the metabolism of the electrogenic microorganisms. The reformulation contained 1 g L - 1Taking the solution of cobalt, strontium, cesium, lanthanum and cerium ions as nuclear wastewater, and diluting the nuclear wastewater to different concentrations (the concentrations are respectively 5 mg L) - 1、10 mg L - 1、20 mg L - 1) The cathode chamber was charged and the system was tested for performance in handling cerium ions and the results are shown in figure 2. Therefore, the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode can effectively reduce cerium ions and basically realize the complete removal of cerium.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation process of a carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode is characterized by comprising the following steps:
(1) pretreatment of the 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 metal organic framework structure of zirconium on the surface of the carbon felt obtained in the step (2) by a hydrothermal method; then, iron, magnesium and zirconium were oxidized by calcination.
2. The preparation process of the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode according to claim 1, wherein in the step (1), the specific step of removing impurities attached to the carbon felt is 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 ℃.
3. The process for preparing a carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode according to claim 1, wherein in the step (1), the etching treatment comprises the following specific steps: the dried carbon felt was immersed in dilute acid, etched for 12-24 h and dried at 60-100 ℃ to create catalyst attachment sites.
4. The preparation process of the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode according to claim 1, wherein 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, dissolving chitosan in dilute acid, stirring for 12-24 h to form viscous solution, adding ferric trichloride hexahydrate and magnesium chloride hexahydrate in the stirring process, wherein 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); and (2) transferring the viscous solution into a reaction kettle, putting the carbon felt obtained in the step (1), performing hydrothermal treatment for 12 hours in a 180 ℃ oven, and finally, washing the carbon felt with deionized water and drying at 60-100 ℃.
5. The process for preparing a carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode according to claim 1, wherein in the step (3), the step of loading the metal-organic framework structure of zirconium on the surface of the carbon felt obtained in the step (2) by a hydrothermal method comprises the specific steps of: 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 performing hydrothermal treatment in a 120 ℃ oven for 24 hours; then, the carbon felt was washed with absolute ethanol and DMF and dried at 60-100 ℃ to remove unreacted materials.
6. The process for preparing a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode as claimed in claim 1, wherein in the step (3), the step of oxidizing iron, magnesium and zirconium by calcination comprises the following specific steps: controlling the heating rate to be 5 ℃ for min- 1And calcining at 600 ℃ for 120 min.
7. The carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode is prepared by adopting the preparation process of the carbon felt-based iron/magnesium/zirconium/nitrogen-doped carbon catalytic electrode as described in any one of claims 1 to 6.
8. Use of a carbon felt-based iron/magnesium/zirconium/nitrogen doped carbon catalytic electrode according to claim 7 for treating nuclear waste water.
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