CN115650373A - Preparation and application of efficient wastewater treatment electrode material - Google Patents
Preparation and application of efficient wastewater treatment electrode material Download PDFInfo
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- CN115650373A CN115650373A CN202211293474.0A CN202211293474A CN115650373A CN 115650373 A CN115650373 A CN 115650373A CN 202211293474 A CN202211293474 A CN 202211293474A CN 115650373 A CN115650373 A CN 115650373A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 229940082569 selenite Drugs 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229960002135 sulfadimidine Drugs 0.000 claims description 6
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 159000000009 barium salts Chemical class 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000003120 macrolide antibiotic agent Substances 0.000 claims description 2
- 229940041033 macrolides Drugs 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 150000007660 quinolones Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 150000003456 sulfonamides Chemical class 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 229940040944 tetracyclines Drugs 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- -1 selenite modified graphite Chemical class 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000005273 aeration Methods 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NIWQQYJSLXQOCI-UHFFFAOYSA-L [O--].[K+].[Ti+4].[O-]C(=O)C([O-])=O Chemical compound [O--].[K+].[Ti+4].[O-]C(=O)C([O-])=O NIWQQYJSLXQOCI-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- HNZYCXDYRNOVLJ-UHFFFAOYSA-L cobalt(2+);selenite Chemical compound [Co+2].[O-][Se]([O-])=O HNZYCXDYRNOVLJ-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention is applicable to the technical field of electrode material preparation and electro-catalysis wastewater treatment, and provides a preparation method of a selenite modified graphite electrode material and application thereof in wastewater treatment, wherein the preparation method of the selenite modified graphite electrode comprises the following steps: hydrothermal synthesis to obtain synthetic material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 Mixing the nano material with a certain amount of PTFE emulsion to obtain a mixed solution, coating the mixed solution on a pretreated graphite plate, and calcining to obtain the electrode material. The electrode is applied to electrochemical advanced oxidationThe treatment technology is used for treating the organic dye wastewater difficult to degrade. The hydrogen peroxide generated by the rapid reduction of oxygen in situ at the cathode is rapidly decomposed into OH and O 2‑ To degrade organic contaminants. The synthesis of the electrode material disclosed by the invention has the advantages of simple process, low energy consumption and large-scale preparation, and has wide industrial application in the field of sewage treatment.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation and electrocatalysis application, and particularly relates to preparation and application of an efficient wastewater treatment electrode material.
Background
Hydrogen peroxide is an environment-friendly oxidant and is widely applied to industries such as bleaching, sewage treatment, groundwater remediation and chemical substance synthesis. At present, the synthesis of hydrogen peroxide is mainly based on an anthraquinone method, and the hydrogen peroxide is extracted and recovered through hydrogenation and oxidation of an alkyl anthraquinone precursor. However, this method is not environmentally friendly and the cost of transporting and storing hydrogen peroxide is high. Compared with the anthraquinone method, the electrochemical synthesis of hydrogen peroxide, which is green and environment-friendly, has low cost and simple process, is widely concerned.
The basic principle of electrochemical synthesis of hydrogen peroxide is via 2-electron O 2 The hydrogen peroxide is synthesized by an electro-reduction reaction as follows:
O 2 +2H + +2e - →H 2 O 2
the cathode is the determining factor for improving the electrochemical synthesis of hydrogen peroxide. Currently, carbon-based cathode materials are most widely used, such as graphite felt, carbon felt, activated carbon fibers, graphite plates, and the like. The graphite has good conductivity and stability, low cost and wide source, but the graphite is used as the cathode to reduce O 2 The activity of hydrogen peroxide generation is poor.
At present, the graphite is modified to efficiently produce hydrogen peroxide, and the modification mainly comprises doping atom (O, N, S, P and the like) modification, external hydrophobic modification and the like. Doping atom modification can increaseAdding graphite to increase the charge density of graphite to make carbon atom in an electrically deficient state, resulting in uneven charge distribution 2 Reduced catalytic activity, but not improved graphite electrode pair O 2 Adsorption of (2) resulting in O 2 The utilization rate of (a) is not high. External hydrophobic modification is generally performed by coating Polytetrafluoroethylene (PTFE) on the surface of graphite, and the hydrophobic property of PTFE is utilized to improve O 2 The adsorption of (2) and then high-efficiently produce hydrogen peroxide, but the coating of PTFE increases the resistance of graphite and is not beneficial to the transfer of electrons.
Therefore, it is highly desirable to develop a method for accelerating proton-coupled electron transfer, O 2 The novel graphite modified cathode has high utilization rate, and can stably and efficiently produce hydrogen peroxide.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and title of the application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the high-efficiency wastewater treatment electrode material.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of an electrode material for efficient wastewater treatment is characterized by comprising the following steps:
dropwise adding selenite solution into cobalt salt solution, magnetically stirring for 30min, adjusting pH with ammonia water, stirring, and synthesizing by hydrothermal method to obtain synthetic material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 ；
The synthesized material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 With 60% solids PTFE emulsion according to 1:15 (w/v) mixing under ultrasound to obtain a mixed solution;
pretreatment of a graphite plate: immersing a graphite plate in acetone, ultrasonically cleaning for 1h, washing for 3-5 times by using deionized water, drying in an oven at the temperature of 80 +/-1 ℃ to constant weight, taking out and cooling for later use;
the mixed solution is coated on a pretreated graphite plate and then calcined for 2 hours at 350 ℃.
As a preferable embodiment of the preparation method of the present invention, wherein: the cobalt salt comprises at least one of nitrate, chloride, sulfate, phosphate, acetate and carbonate.
As a preferable embodiment of the preparation method of the present invention, wherein: the selenite comprises at least one of ammonium salt, lithium salt, sodium salt, potassium salt, magnesium salt and barium salt.
As a preferable embodiment of the preparation method of the present invention, wherein: and ammonia water is used for adjusting the pH value of the solution to 5-10.
As a preferable embodiment of the preparation method of the present invention, wherein: the ratio of the cobalt salt to the selenite is 0.1-10: 0.1 to 10.
As a preferable embodiment of the preparation method of the present invention, wherein: the hydrothermal synthesis temperature is 100-200 ℃, and the reaction time is more than 1 hour.
As a preferable embodiment of the preparation method of the present invention, wherein: the calcination of the graphite plate is carried out in a muffle furnace, the temperature is controlled to be 200-400 ℃, and the calcination time is more than 2 hours.
Still another object of the present invention is to solve the disadvantages of the prior art and to provide an application of the electrode material for high efficiency wastewater treatment.
In order to solve the technical problems, the invention provides the following technical scheme: the electrolyte solution used when the electrode material is used for treating wastewater is a phosphoric acid buffer solution or a sulfate aqueous solution containing organic dye or antibiotic which are difficult to degrade, the pH range is 6-14, and the applied voltage range is-1.5V.
As a preferable mode of the application of the present invention, wherein: the organic chloride, the organic phosphorus pesticide, the organic heavy metal compound, the polycyclic and other long-chain organic compound organic dyes represented by aromatics or antibiotics comprise at least one of methyl blue, methyl orange, rhodamine B, sulfamethazine, tetracyclines, quinolones, sulfonamides, macrolides and chloramphenical.
As a preferable aspect of the application of the present invention, wherein: the electrode material is used in the fields of wastewater treatment, hydrogen peroxide preparation by electrocatalytic reduction, new energy and devices
The invention has the beneficial effects that:
the invention provides a simple and convenient loaded Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 By means of PTFE and the material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 The graphite plate is uniformly mixed and coated on the surface of the graphite plate for preparation, and the preparation method is simple in preparation steps and high in stability. Material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 The synthesis is simple, and only certain concentration of CoCl is needed 2 ·6H 2 O and SeO 2 Mixing the raw materials according to the proportion, and carrying out hydrothermal treatment for two days to obtain the product. Further, the material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 And mixing the graphite powder and a PTFE solution in proportion, coating the mixture on the surface of a graphite plate, and calcining the graphite plate to obtain the modified graphite electrode. Selecting Co as material 12 (OH) 2 (SeO 3 ) 8 (OH) 6 As a load material, the metal cobalt and selenite are utilized to promote proton coupling electron transfer, and simultaneously, PTFE is used as a binder of the material and a graphite plate, so that the stability of the graphite plate is enhanced, the hydrophobic property of the graphite plate is improved, and O is facilitated 2 Adsorption of (2), increase of O 2 The utilization ratio of (c).
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 shows Co in example 1 of the present invention 12 (OH) 2 (SeO 3 ) 8 (OH) 6 Powder diffraction patterns of the material and the modified graphite electrode thereof.
Fig. 2 is SEM images (a to d) and distribution diagrams (e to h) of elements O, co, se of the modified graphite electrode in example 2 of the present invention.
FIG. 3 is a diagram of an apparatus for electrochemically synthesizing hydrogen peroxide in example 3 of the present invention.
FIG. 4 is a graph showing the relationship between the concentration of hydrogen peroxide and the aeration rate in example 4 of the present invention.
FIG. 5 is a graph showing the relationship between hydrogen peroxide concentration and current density in example 4 of the present invention.
FIG. 6 is a graph of hydrogen peroxide concentration versus pH verified in example 4 of the present invention.
FIG. 7 is a graph showing the effect of the electrode material in example 5 of the present invention in recycling methyl blue-containing wastewater.
FIG. 8 shows the degradation efficiency of the electrode material containing sulfamethazine treated by the electrode material in example 6 of the present invention in different systems (a) and different quenching experiments.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
EXAMPLE 1 preparation of electrode Material
The invention is further illustrated below with reference to two examples:
as shown in FIG. 1, co of example 1 of the present invention 12 (OH) 2 (SeO 3 ) 8 (OH) 6 The material synthesis comprises the following specific steps:
(1) 16.6mmol of CoCl 2 ·6H 2 O was dissolved in 7mL deionized water, stirred continuously until the solution was well mixed, and pH =6 was adjusted with pure ammonia to give solution D.
(2) 11.2mmol of SeO 2 Dissolved in 20mL of deionized water, and the pH =6 was adjusted in the same manner as in step (1), to obtain solution E.
(3) And dropwise adding the solution E into the solution D under continuous stirring, and continuously stirring for 30min to obtain a mixed solution.
(4) Transferring the mixed solution obtained in the step (3) into a 50mL PTFE-lined hydrothermal reaction kettle, transferring the reaction kettle into a 180 +/-1 ℃ drying oven, reacting for 2 days, controlling the cooling rate at 5 +/-1 ℃/h, cooling to room temperature, taking out particles, washing with absolute ethyl alcohol and deionized water for 3 times, and finally placing in a 105 +/-1 ℃ drying oven to obtain Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 A material.
The preparation method of the cobalt selenite modified graphite electrode comprises the following specific steps:
(1) 0.1g of Co in example 1 12 (OH) 2 (SeO 3 ) 8 (OH) 6 The material and PTFE emulsion with solid content of 1.5mL60% are mixed in ultrasonic to obtain mixed solution.
(2) Immersing a graphite plate with the size of 2.5cm x 0.1cm in a 1mol/L acetone solution, ultrasonically cleaning for 1h, washing for 3-5 times by using deionized water until the acetone is completely washed, and transferring into a drying oven with the temperature of 105 +/-1 ℃ for drying for later use.
(3) And (2) uniformly coating the mixed solution obtained in the step (1) on the pretreated graphite plate by using a brush for 3 times, transferring the mixed solution into a muffle furnace at 350 +/-10 ℃ for calcining for 2 hours after each coating for 1 time, and finally obtaining the graphite modified cathode for efficiently producing the hydrogen peroxide. The selenite electrode material prepared by the method is consistent with a theoretical fitting peak by determining a powder diffraction pattern, which shows that the selenite is successfully loaded on the graphite electrode and the prepared material has high purity.
EXAMPLE 2 morphological characterization of samples
Characterization tests were performed on the prepared sample morphology by SEM, as shown in fig. 2. The prepared cobalt selenite material has a nano-rod-shaped structure, the length is micron-sized, the diameter is nano-sized, and the appearance is uniform. And as shown in figure 2, eds spectrum analysis chart, it is evident that uniform spatial distribution of Co, se and O on the nanowires further determines the composition of the prepared material.
EXAMPLE 3 wastewater treatment apparatus
In order to verify the stability and the high efficiency of the modified graphite cathode prepared by the method, the following method is specially selected for verification. The experimental apparatus is shown in fig. 3, the volume of the whole experimental apparatus is 400mL, the cathode and the anode are not separated, the anode adopts a carbon brush 1, the cathode adopts a modified graphite cathode 3 prepared by the invention, the electrolyte solution is a sodium sulfate solution 4, the concentration of the sodium sulfate solution is 0.05mol/L, the volume of the sodium sulfate solution is 300mL, the peristaltic pump 5 is adopted to continuously aerate the cathode, and the power supply adopts a direct current power supply 2. The high-efficiency hydrogen peroxide-producing modified graphite electrode prepared by the invention is used as a cathode to carry out an electrolysis experiment in the device.
Example 4 production of Hydrogen peroxide by cobalt selenite-modified graphite electrode
The results of the experiments are shown in FIGS. 4, 5 and 6, and the current density in FIG. 4 is 7mA/cm 2 The electrolyte solution was run under conditions of pH =3, and fig. 4 is a graph of the hydrogen peroxide generation concentration versus the cathode aeration rate. Experimental results show that the cathode aeration rate is 0mL/min, the hydrogen peroxide concentration in electrolysis for 120min is 35.1mg/L, the hydrogen peroxide concentration is increased along with the increase of the aeration rate, when the aeration rate is 6mL/min, the hydrogen peroxide concentration in electrolysis for 120min is 52.3mg/L, and the hydrogen peroxide concentration is increased by 0.49 times compared with that in the case of no aeration, which indicates that the modified graphite cathode electrode prepared by the invention is O 2 Has good adsorption effectAnd the aeration rate of 6mL/min is very low, and the energy consumption is not high, which shows that the modified graphite cathode prepared by the invention can efficiently produce hydrogen peroxide at the very low aeration rate. When the aeration rate is 8mL/min, the hydrogen peroxide concentration is 38.6mg/L after electrolysis for 120min, and the relatively highest hydrogen peroxide concentration is reduced by 13.7mg/L, probably because the aeration rate is too high, bubbles are enlarged, and the cathode is not beneficial to O 2 The adsorption is carried out, the synthesis of the hydrogen peroxide is influenced, and the aeration rate of 8mL/min is increased relative to the energy consumption of 6 mL/min. Therefore, in the application of the modified graphite cathode prepared by the invention, a proper aeration rate is selected, so that not only can energy consumption be saved, but also hydrogen peroxide can be efficiently synthesized. Fig. 5 is performed under the conditions of an aeration rate of 6mL/min and pH =3 of the electrolyte solution, and fig. 5 is a graph of a hydrogen peroxide generation concentration versus a current density. The experiment result shows that the concentration of the hydrogen peroxide is gradually increased along with the current density, and when the current density is too high, the O can be inhibited 2 Two electrons reduce hydrogen peroxide to promote O 2 The four electrons are reduced to produce water, and meanwhile, the current density is overlarge, the energy consumption is increased, and the cost is increased. Therefore, in the application of the modified graphite cathode prepared by the invention, the proper current density is selected, the cost is saved, and simultaneously, the hydrogen peroxide can be efficiently produced. FIG. 6 at a current density of 7mA/cm 2 The aeration rate was set at 6mL/min, and FIG. 6 is a graph showing the relationship between the hydrogen peroxide concentration and the pH of the electrolyte solution. Experimental results show that the modified graphite cathode prepared by the invention can stably and efficiently produce hydrogen peroxide under different pH values, and has the best hydrogen peroxide production effect when the pH value is =3.
Example 5 treatment of methyl blue-containing wastewater with cobalt selenite-modified graphite electrode
The cobalt selenite-modified graphite electrode was placed in a solution containing 20.0 mg/l methyl blue, 0.05M phosphate buffer (pH = 3.0), and 0.05M Na 2 SO 4 In the electrolyte of (1). At regular intervals, 3.0ml of the solution was taken, and pH and H were measured with a pH analyzer (LAQUAtwin-PH-33, japan), a titanium potassium oxalate method and an ultraviolet spectrophotometer (wavelength: 664 nm), respectively 2 O 2 And methyl blue concentration, as shown in FIG. 7, the electrode can be used within 90 minutesCompletely degrades methyl blue (nearly 100 percent), and the final removal rate can still reach 92.1 percent after 10 cycles. This means that the catalyst maintains good stability and active sites during degradation.
Example 6 treatment of wastewater containing antibiotic and sulfa-methyl pyrimidine with electrode of cobalt selenite-modified graphite
Placing the cobalt selenite modified graphite electrode in a container containing 20.0 mg/L sulfamethazine and 0.05M0.05M Na 2 SO 4 In the electrolyte of (1). Samples of 3.0mL were taken every 10 minutes. The pH and H in the sample were measured by a pH analyzer (LAQUAtwin-PH-33, japan), a titanium oxide potassium oxalate method and high performance liquid chromatography, respectively 2 O 2 And sulfamethazine concentration. After 90 minutes of degradation, 3 ml samples were taken and their concentration measured by HPLC and UV spectrophotometer (664 nm-MB). As shown in FIG. 8, the electrode can also completely degrade the sulfamethazine concentration (close to 100%), and the final removal rate can still reach 92.1% after 10 cycles. This means that the catalyst maintains good stability and active sites during degradation.
Therefore, the invention discloses a preparation method of a graphite modified cathode for efficiently producing hydrogen peroxide, and belongs to the technical field of environmental engineering. The invention adopts synthetic material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 The modified graphite electrode is prepared by uniformly coating the mixture of the modified graphite electrode and PTFE on the surface of graphite after mixing, and can efficiently produce hydrogen peroxide in the electrolytic process, and the maximum hydrogen peroxide of 52.3mg/L can be produced by 120min of electrolysis. The preparation process of the invention is simple, and the electrolysis condition (aeration rate 6mL/min, pH =3, current density 7 mA/cm) for efficiently producing hydrogen peroxide is adopted 2 ) Low requirement, low energy consumption and low cost.
In order to better explain the present invention and facilitate comparison of technical effects of different reaction systems, transition metal cobalt and copper salt are selected in the following examples for corresponding illustration. However, it should be noted that these examples are only for illustrating the present application and are not meant to limit the scope of the present application, and other transition metals such as iron, cobalt, nickel, copper salts, such as acetate, sulfate, chloride, phosphate, carbonate, etc., have the same characteristics and principles as the following examples, and thus all fall within the protection scope of the present invention.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of an electrode material for efficient wastewater treatment is characterized by comprising the following steps:
dropwise adding selenite solution into cobalt salt solution, magnetically stirring for 30min, adjusting pH with ammonia water, uniformly stirring, and synthesizing by hydrothermal method to obtain synthetic material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 ；
The synthesized material Co 12 (OH) 2 (SeO 3 ) 8 (OH) 6 With 60% solids PTFE emulsion according to 1:15 (w/v) mixing under ultrasound to obtain a mixed solution;
pretreatment of a graphite plate: immersing a graphite plate in acetone, ultrasonically cleaning for 1h, washing for 3-5 times by using deionized water, drying in an oven at the temperature of 80 +/-1 ℃ to constant weight, taking out and cooling for later use;
the mixed solution is coated on a pretreated graphite plate and then calcined for 2 hours at 350 ℃.
2. The method for preparing the electrode material for high-efficiency wastewater treatment according to claim 1, wherein the method comprises the following steps: the cobalt salt comprises at least one of nitrate, chloride, sulfate, phosphate, acetate and carbonate.
3. The method for preparing the graphite modified cathode for efficiently producing hydrogen peroxide according to claim 1, wherein the graphite modified cathode comprises the following components: the selenite comprises at least one of ammonium salt, lithium salt, sodium salt, potassium salt, magnesium salt and barium salt.
4. The method for preparing the electrode material for high efficiency wastewater treatment according to claim 1, wherein the method comprises the following steps: and ammonia water is used for adjusting the pH value of the solution to 5-10.
5. The method for preparing the electrode material for high-efficiency wastewater treatment according to any one of claims 1 to 4, wherein the method comprises the following steps: the ratio of the cobalt salt to the selenite is 0.1-10: 0.1 to 10.
6. The method for preparing the electrode material for high-efficiency wastewater treatment according to claim 1, wherein the method comprises the following steps: the hydrothermal synthesis temperature is 100-200 ℃, and the reaction time is more than 1 hour.
7. The method for preparing the electrode material for high efficiency wastewater treatment according to claim 1, wherein: the calcination of the graphite plate is carried out in a muffle furnace, the temperature is controlled to be 200-400 ℃, and the calcination time is more than 2 hours.
8. The application of the electrode material for high-efficiency wastewater treatment prepared by the preparation method according to any one of claims 1 to 7, which comprises the following steps: the electrolyte solution used when the electrode material is used for treating wastewater is a phosphoric acid buffer solution or a sulfate aqueous solution containing organic dye or antibiotic which are difficult to degrade, the pH range is 6-14, and the applied voltage range is-1.5V.
9. The use of the electrode material for high efficiency wastewater treatment according to claim 8, wherein the organic chloride, organic phosphorus pesticide, organic heavy metal compound, polycyclic and other long-chain organic compound organic dye or antibiotic represented by aromatic group comprises at least one of methyl blue, methyl orange, rhodamine B, sulfamethazine, tetracyclines, quinolones, sulfonamides, macrolides and chloramphenical group.
10. The use of an electrode material for efficient wastewater treatment according to claim 8, comprising: the electrode material is used in the fields of wastewater treatment, hydrogen peroxide preparation by electrocatalytic reduction, new energy and devices.
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