CN117535684B - Electrode assembly of electrolytic cell, electrolytic cell device for producing hydrogen peroxide and application thereof - Google Patents
Electrode assembly of electrolytic cell, electrolytic cell device for producing hydrogen peroxide and application thereof Download PDFInfo
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- CN117535684B CN117535684B CN202410026681.2A CN202410026681A CN117535684B CN 117535684 B CN117535684 B CN 117535684B CN 202410026681 A CN202410026681 A CN 202410026681A CN 117535684 B CN117535684 B CN 117535684B
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- hydrogen peroxide
- carbon
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- oxygen
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 240
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 156
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000010439 graphite Substances 0.000 claims abstract description 99
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 99
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 78
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 70
- 239000001301 oxygen Substances 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 19
- 239000008399 tap water Substances 0.000 claims abstract description 18
- 235000020679 tap water Nutrition 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000750 progressive effect Effects 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 52
- 229910001220 stainless steel Inorganic materials 0.000 claims description 37
- 239000010935 stainless steel Substances 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- 238000004659 sterilization and disinfection Methods 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- 238000001471 micro-filtration Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000004887 air purification Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims 1
- 229910006299 γ-FeOOH Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000007769 metal material Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 5
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 26
- 230000001954 sterilising effect Effects 0.000 description 23
- 230000008569 process Effects 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 239000000645 desinfectant Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 230000002035 prolonged effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 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 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 230000001332 colony forming effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000003206 sterilizing agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000005418 spin wave Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
- A61L2/186—Peroxide solutions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/14—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes
- A61L9/145—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes air-liquid contact processes, e.g. scrubbing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/10—Apparatus features
- A61L2202/11—Apparatus for generating biocidal substances, e.g. vaporisers, UV lamps
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
- A61L2209/20—Method-related aspects
- A61L2209/21—Use of chemical compounds for treating air or the like
- A61L2209/211—Use of hydrogen peroxide, liquid and vaporous
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
An electrode assembly for an electrolytic cell, an electrolytic cell apparatus for producing hydrogen peroxide and use thereof, the electrode assembly for an electrolytic cell comprising: a cathode and an anode; the cathode is a carbon-based material rich in nitrogen and oxygen functional groups, and provides an electro-catalysis effect for the reaction of reducing oxygen into hydrogen peroxide; the carbon-based material rich in nitrogen and oxygen functional groups is prepared by progressive oxidation: firstly, immersing a first carbon-based material into acid liquor for pre-oxidation, secondly, performing electrooxidation treatment in tap water or a solution containing acid, alkali and salt, converting graphite nitrogen of a second carbon-based material into pyridine nitrogen and pyrrole nitrogen, and generating carboxyl and carbon-oxygen double bonds. The anode is in-situ electrochemical activated metal material, the surface is rich in metal oxide and hydroxyl oxide, and the catalysis is provided for oxygen precipitation reaction. The electrode assembly of the electrolytic cell can be used for directly and electrochemically reducing oxygen to produce hydrogen peroxide, is convenient to use, and can realize higher hydrogen peroxide yield and higher current efficiency under lower current density.
Description
Technical Field
The invention relates to the technical field of electrolytic cells, in particular to an electrode assembly of an electrolytic cell, an electrolytic cell device for producing hydrogen peroxide and application thereof.
Background
Hydrogen peroxide (H 2O2, the aqueous solution of which is commonly called hydrogen peroxide) is a disinfectant with higher efficiency, convenient use, no toxicity and no corrosiveness. The production method of hydrogen peroxide mainly comprises an electrolysis method, an anthraquinone method, an isopropanol method, an oxygen cathode reduction method, an oxyhydrogen direct oxidation method and the like, wherein the anthraquinone method is a main method for producing hydrogen peroxide, but the traditional anthraquinone method has complex process, high energy consumption and produces a large amount of toxic byproducts.
Compared with the most commonly used anthraquinone method at present, the in-situ production of the hydrogen peroxide disinfectant can be realized based on the oxygen cathode reduction method in an electrochemical system, the hydrogen peroxide disinfectant generated in situ through the two-electron oxygen reduction reaction has higher activity and better sterilization effect than the hydrogen peroxide disinfectant generated by the traditional method, but the cathode stability is poor and generally only can be stabilized for tens of hours when the oxygen cathode reduction method is used in the related technology, so that the practical requirement is difficult to meet. In addition, in the related art, the electrolyte is selected from sulfuric acid, potassium hydroxide, sodium sulfate and other solutions with certain concentrations, so that the cost is increased, the application scene is greatly limited, and the use is inconvenient.
Disclosure of Invention
In view of the above-mentioned problems, the present invention provides an electrode assembly for an electrolytic cell, an electrolytic cell device for producing hydrogen peroxide and use thereof, in order to at least partially solve at least one of the above-mentioned problems.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
As one aspect of the present invention, there is provided an electrode assembly of an electrolytic cell, comprising: a cathode and an anode; the cathode comprises a carbon-based material rich in nitrogen and oxygen functional groups to provide an electrocatalytic effect for the reduction of oxygen to hydrogen peroxide; the carbon-based material rich in nitrogen and oxygen functional groups is prepared by progressive oxidation: immersing the first carbon-based material in a nitric acid solution, and performing pre-oxidation treatment for 3-9 hours at 50-100 ℃ to obtain a hydrophilic second carbon-based material; and (3) performing electrooxidation treatment on the second carbon-based material for 10-30 min to convert graphite nitrogen in the second carbon-based material into pyridine nitrogen and pyrrole nitrogen and generate carboxyl and carbon-oxygen double bonds, wherein the first carbon-based material comprises at least one of graphite felt, carbon fiber felt, nitrogen doped carbon and the like, the electrolyte of the electrooxidation treatment comprises tap water, or the electrolyte of the electrooxidation treatment comprises an acid-containing solution, an alkali-containing solution or a salt-containing solution.
According to some embodiments of the invention, the anode material comprises an anodized activated metal material, which provides a catalyst for the oxygen evolution reaction, the anode surface is a metal oxide and a metal oxyhydroxide, and the electrolyte of the electrolytic cell is tap water.
According to some embodiments of the invention, the first carbon-based material is subjected to a sequential ultrasonic, water washing and drying treatment prior to immersing the first carbon-based material in the acid solution.
According to some embodiments of the invention, the cathode and anode are configured to be reactivated by alternating the anode and cathode.
According to some embodiments of the present invention, the electrode assembly includes a plurality of cathodes and 2 anodes, the 2 anodes are arranged in parallel at intervals, the plurality of cathodes are respectively and vertically arranged between the 2 anodes and are arranged in parallel at intervals along an extending direction of the anodes, the metal material includes a stainless steel material, the anodes are configured as a mesh structure, and mesh numbers of the mesh structure are 1000-3500.
As another aspect of the present invention, there is provided an electrolytic cell device for producing hydrogen peroxide, comprising: a closed container for accommodating an electrolyte; the electrode assembly as described above, disposed in the closed container; the driving assembly is communicated with the closed container and is suitable for conveying air to the cathode of the electrode assembly, so that oxygen in the air is reduced into hydrogen peroxide under the electrocatalytic action of the cathode; the power supply controller is electrically connected with the electrode assembly and is suitable for providing electron flow for the electrode assembly; and a separator disposed between the cathode and the anode of the electrode assembly for preventing the hydrogen peroxide from being transferred to the anode so that the hydrogen peroxide is decomposed.
According to some embodiments of the invention, the drive assembly comprises: a driving pump for blowing air; one end of the air duct is communicated with the driving pump, and the other end of the air duct is connected to the cathode and is suitable for conveying air blown in by the driving pump to the bottom of the cathode.
According to some embodiments of the invention, the membrane comprises a mixed cellulose microfiltration membrane or ion exchange membrane having a pore size of 0.1-1 μm.
According to some embodiments of the invention, the power of the driving pump is 15-100W, and the air flow rate of the driving pump is 20-100L/min; the DC voltage of the power supply controller is 12-96V.
As a further aspect of the invention there is provided a use in an electrolytic cell device as described above for achieving water purification, air purification, odour removal and disinfection cleaning.
Based on the technical scheme, the electrode assembly of the electrolytic cell, the electrolytic cell device for producing hydrogen peroxide and the application thereof have at least one or a part of the following beneficial effects:
According to the method, the first carbon-based material is immersed in the nitric acid solution for pre-oxidation treatment, and carbon atoms on the surface of the first carbon-based material can be oxidized to form oxygen-containing functional groups due to the strong oxidizing property of nitric acid. The introduced oxygen-containing functional groups have polarity and can generate hydrogen bond interaction with water molecules in the electrolyte, so that the interaction force between the surface of the first carbon-based material and the electrolyte is improved, the hydrophilic performance of the first carbon-based material is enhanced, and when the first carbon-based material contacts with the electrolyte, electron transfer between the first carbon-based material and the electrolyte is facilitated, so that the hydrophilic second carbon-based material is formed. Further, when tap water or various solutions containing salt, acid and alkali are subjected to electrooxidation treatment, graphite nitrogen in the hydrophilic second carbon-based material is converted into pyridine nitrogen and pyrrole nitrogen under the action of anode potential, and more carboxyl and carbon-oxygen double bond groups are generated on the surface of the hydrophilic second carbon-based material. After progressive oxidation treatment is carried out on the carbon-based material, functional groups are obviously increased, microscopic morphology is greatly changed, compared with untreated carbon-based material, surface ravines of the carbon-based material rich in nitrogen and oxygen functional groups are increased, roughness is increased, irregular distribution states are presented, defects are increased, the reaction activity area is increased, and hydrogen peroxide is generated by the oxygen reduction reaction.
The invention activates the netlike metal material by anodic in-situ electrooxidation, and the metal oxide or hydroxyl oxide generated on the surface of the metal provides a catalytic active site for oxygen precipitation reaction, and simultaneously protects the internal metal.
The cathode and anode materials of the electrode assembly prepared by the invention have stable properties and lower cost, and are beneficial to large-scale application.
The hydrogen peroxide generated by electrochemical action of the electrolytic cell device for producing hydrogen peroxide is ready to use, has better disinfection and sterilization effect compared with manual configuration effect, does not harm human body, and is not easy to cause toxic residue after disinfection.
Drawings
FIG. 1 is a schematic cross-sectional view of an electrolytic cell device according to an embodiment of the present invention;
FIG. 2 is a schematic perspective view of an electrolytic cell device according to an embodiment of the present invention;
FIG. 3a is a scanning electron microscope image of the original graphite felt of example 1 of the present invention;
FIG. 3b is a scanning electron microscope image of a graphite felt enriched in nitrogen and oxygen functional groups of example 1 of the present invention;
FIG. 4 is a Raman spectrum comparison of the original graphite felt of example 1 of the present invention and a graphite felt rich in nitrogen and oxygen functional groups;
FIG. 5a is an X-ray photoelectron carbon spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention;
FIG. 5b is an X-ray photoelectron spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention;
FIG. 5c is an X-ray photoelectron spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention;
FIG. 6a is a scanning electron microscope image of the original stainless steel mesh of example 2 of the present invention;
FIG. 6b is a scanning electron microscope image of an electro-oxidized stainless steel mesh of example 2 of the present invention;
FIG. 7 is a graph comparing Raman spectra of the original stainless steel mesh and the electro-oxidized stainless steel mesh of example 2 of the present invention;
FIG. 8 is a graph showing the variation in the yield and current efficiency of hydrogen peroxide produced at various current densities in example 3 of the present invention;
FIG. 9 is a histogram of the yield of hydrogen peroxide produced at various reaction times in example 3 of the present invention;
FIG. 10 is a graph showing the variation in hydrogen peroxide production and current efficiency produced when using different electrolytes according to example 4 of the present invention;
FIG. 11 is a graph of hydrogen peroxide yield and current efficiency variation generated using different membrane types for example 5 of the present invention;
FIG. 12 is a histogram of hydrogen peroxide yields generated in example 6 of the present invention when different cathode materials are used;
FIG. 13 is a histogram of change in electrode stability test for example 7 of the present invention;
FIG. 14 is a schematic view showing the effect of sterilization by hydrogen peroxide produced in example 8 of the present invention;
Fig. 15 is a schematic view showing the sterilizing effect of hydrogen peroxide manually formulated in comparative example 1 of the present invention.
[ Reference numerals description ]
1-A cathode;
2-anode;
3-a closed container;
4-a drive assembly;
41-driving a pump;
42-an airway;
421-air outlet;
5-a power supply controller;
6-a membrane;
7-cathode lead;
8-anode lead.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
It should be understood that the description is only illustrative and is not intended to limit the scope of the application. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the application. It may be evident, however, that one or more embodiments may be practiced without these specific details. In the following description, descriptions of well-known techniques are omitted so as not to unnecessarily obscure the concept of the present application.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "comprising" as used herein indicates the presence of a feature, step, operation, but does not preclude the presence or addition of one or more other features.
Where a convention analogous to "at least one of A, B and C, etc." is used, in general such a convention should be interpreted in accordance with the meaning of one of skill in the art having generally understood the convention (e.g., "a system having at least one of A, B and C" would include, but not be limited to, systems having a alone, B alone, C alone, a and B together, a and C together, B and C together, and/or A, B, C together, etc.). Where a formulation similar to at least one of "A, B or C, etc." is used, in general such a formulation should be interpreted in accordance with the ordinary understanding of one skilled in the art (e.g. "a system with at least one of A, B or C" would include but not be limited to systems with a alone, B alone, C alone, a and B together, a and C together, B and C together, and/or A, B, C together, etc.).
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.
When the oxygen cathode reduction method is used, the cathode electrode material in the related art is poor in stability and usually only can be stabilized for tens of hours, so that the practical requirements are difficult to meet, and the use of the electrolyte is increased by adopting a salt solution such as sulfuric acid, potassium hydroxide or sodium sulfate, and the like, so that the cost is increased and the use is inconvenient. In the process of realizing the invention, the carbon-based cathode is changed into the carbon-based cathode rich in nitrogen and oxygen functional groups through modification, so that the stability of hydrogen peroxide preparation can be improved, the electrolysis process can be simplified, the use is more convenient, and the industrial popularization is facilitated.
In view of this, the present invention proposes an electrode assembly of an electrolytic cell, an electrolytic cell device for producing hydrogen peroxide comprising the same, and applications thereof, which converts graphite nitrogen in a second carbon-based material into pyridine nitrogen and pyrrole nitrogen under the action of an anode potential while generating more carboxyl and carbon-oxygen double bond groups on the surface when electrooxidation is performed using tap water, or a solution containing a salt, an acid or a base as an electrolyte. After the first carbon-based material is subjected to hydrophilic and electrooxidation treatment, functional groups are obviously increased, microscopic morphology is greatly changed, and compared with the untreated first carbon-based material, the surface ravines of the carbon-based material rich in nitrogen and oxygen functional groups are increased, the roughness is increased, irregular distribution states are shown, defects are increased, the reaction activity area is increased, and the hydrogen peroxide is generated by the oxygen reduction reaction.
FIG. 1 is a schematic cross-sectional view of an electrolytic cell device according to an embodiment of the present invention. FIG. 2 is a schematic perspective view of an electrolytic cell device according to an embodiment of the present invention.
According to one exemplary embodiment of the present invention, an electrode assembly of an electrolytic cell is provided. Referring to fig. 1 to 2, the method includes: a cathode 1 and an anode 2. The cathode 1 comprises a carbon-based material rich in nitrogen and oxygen functions to provide an electrocatalytic effect for the reduction of oxygen to hydrogen peroxide. The carbon-based material rich in nitrogen and oxygen is prepared by progressive oxidation: and immersing the first carbon-based material into a nitric acid solution, and performing pre-oxidation treatment for 3-9 hours at 50-100 ℃ to obtain the hydrophilic second carbon-based material. And (3) performing electrooxidation treatment on the hydrophilic second carbon-based material for 10-30 min to convert graphite nitrogen in the second carbon-based material into pyridine nitrogen and pyrrole nitrogen, and generating carboxyl and carbon-oxygen double bonds. The first carbon-based material comprises at least one of graphite felt, carbon fiber felt, nitrogen doped carbon, the electrooxidation treated electrolyte comprises tap water, or the electrooxidation treated electrolyte comprises an acid-containing, or alkali-containing or salt-containing solution.
According to some embodiments of the present invention, the first carbon-based material is immersed in the nitric acid solution for pre-oxidation treatment, carbon atoms on the surface of the first carbon-based material can be oxidized due to the strong oxidizing property of nitric acid to form oxygen-containing functional groups, and the introduced oxygen-containing functional groups have polarity and can generate hydrogen bond interaction with water molecules in the electrolyte, so that the interaction force between the surface of the first carbon-based material and the electrolyte is improved, the hydrophilic performance of the first carbon-based material is enhanced, and when the first carbon-based material contacts with the electrolyte, electron transfer between the first carbon-based material and the second carbon-based material is facilitated, so that the hydrophilic second carbon-based material is obtained. Further, in the case of electrooxidation of tap water or various solutions containing salts, acids and bases as an electrolyte, for example, an ammonium oxalate solution may be used as an electrolyte, and graphite nitrogen in the second carbon-based material is converted into pyridine nitrogen and pyrrole nitrogen under the action of an anodic potential while more carboxyl groups and carbon-oxygen double bond groups are generated on the surface. After the progressive oxidation treatment is carried out on the carbon-based material, not only is the functional group obviously increased, but also the microscopic morphology is greatly changed, compared with the untreated first carbon-based material, the surface gully of the carbon-based material rich in nitrogen and oxygen functional groups is increased, the roughness is increased, irregular distribution states are presented, the defects are increased, the reaction activity area is increased, and the hydrogen peroxide is generated by the oxygen reduction reaction.
According to some embodiments of the present invention, the anode 2 includes a metal material that is anodized, and the surface of the anode is a metal oxide and a metal oxyhydroxide, which provide a catalytic effect for oxygen precipitation reaction. The electrolyte of the electrolytic cell is tap water. In the related art, the anode 2 is mainly made of noble metal iridium and ruthenium oxide loaded by metallic titanium, so that the cost is high, and the large-scale application is difficult. The invention adopts stable stainless steel material with low cost and tap water as electrolyte without adding extra salt, thus simplifying the electrolysis process and being more convenient to use. In carrying out experiments related to the present invention, it was found that the effect obtained was relatively better when graphite materials rich in nitrogen and oxygen functional groups were used as the cathode 1.
According to some embodiments of the present invention, the metal material of the anode 2 is ultrasonically treated in an organic solvent to remove organic substances attached to the surface thereof, washed with water, dried, and then placed in an electrolytic cell to perform the electro-oxidation of the anode 2, and the electro-oxidation of the anode 2 is performed under constant current using sodium carbonate as a supporting electrolyte according to need. The anode 2 comprises a metal material subjected to anodic oxidation activation treatment, and provides a catalytic effect for an oxygen precipitation reaction. The metal material is subjected to electrooxidation treatment to produce a layer of compact metal hydroxide or oxyhydroxide on the surface of the anode 2, which has high activity on oxygen precipitation reaction and is inert to hydrogen peroxide decomposition, and simultaneously protects the metal inside the anode 2.
According to some embodiments of the invention, the electrode assembly of the electrolytic cell has stable cathode 1 and anode 2 materials, low cost and is beneficial to large-scale application.
According to some embodiments of the invention, the first carbon-based material is subjected to ultrasonic treatment, water washing and drying treatment in sequence before being immersed in the nitric acid solution. The first carbon-based material is first subjected to ultrasonic treatment in an organic solvent, for example, an ethanol solvent may be used to remove the organic substances adhering to the surface of the first carbon-based material. And then washing the first carbon-based material with water to remove the organic solvent doped on the first carbon-based material, and then drying to ensure the cleaning of the pretreated carbon-based surface.
According to some embodiments of the present invention, the electrode assembly includes a plurality of cathodes 1 and 2 anodes 2, the 2 anodes 2 being arranged in parallel at intervals, and the plurality of cathodes 1 being respectively arranged vertically between the 2 anodes 2 and being arranged in parallel at intervals along the extending direction of the anodes 2. The metal material selected for the anode 2 includes titanium, nickel, stainless steel or copper, preferably stainless steel. The anode 2 is constructed in a mesh structure having a mesh number of 1000 to 3500. Wherein, the cathode 1 can be fixed by a clamping groove, and the anode 2 can be made into a folding structure by adopting a stainless steel net according to the requirement and then inserted into the anode groove. The mesh number of the mesh structure may be 1000, 1500, 2000, 2500, 3000 or 3500, but is not limited thereto.
According to some embodiments of the invention, the cathode 1, anode 2 are configured to be reactivated by alternating the cathodes and anodes. When the related pre-experiments of the invention are carried out, the yield of hydrogen peroxide is slightly reduced after the cathode and anode are used for 500 times, at this time, the cathode 1 and the anode 2 are inverted, namely, a carbon-based material rich in nitrogen and oxygen functional groups is used as the anode 2, an electro-oxidized metal material is used as the cathode 1, and the second carbon-based material is re-oxidized, wherein the oxidation time is 170-190 min, 170min, 180min or 190min, the oxidation current is 50-70 mA, and 50mA, 60mA or 70mA, so that the stability of the electrode assembly can reach 1000 times of cyclic use while the higher hydrogen peroxide yield can be achieved, the service life of the electrode assembly can be effectively prolonged by alternate reactivation of the cathode and the anode, and the service period of the electrode assembly can reach 1-2 years or longer.
According to an embodiment of another aspect of the present invention, there is provided an electrolytic cell apparatus for producing hydrogen peroxide, comprising: and a closed container 3 for containing an electrolyte. The electrode assembly as described above is disposed in the sealed container 3. And a driving assembly 4, which is communicated with the closed container 3 and is suitable for conveying air to the cathode 1 of the electrode assembly, so that oxygen in the air is reduced into hydrogen peroxide under the electrocatalytic action of the cathode 1. And a power supply controller 5 electrically connected to the electrode assembly and adapted to supply the electrode assembly with an electron flow. A separator 6 disposed between the cathode 1 and the anode 2 of the electrode assembly for preventing the hydrogen peroxide from being transferred to the anode 2 so that the hydrogen peroxide is decomposed. In the electrolytic cell device, the electrodes of the cathode 1 and the anode 2 are respectively connected with the cathode and the anode of the power supply controller 5 to form a closed loop, so that the cathode 1 and the anode 2 can respectively provide electron flow.
The reaction principle of the traditional oxygen cathode reduction method for producing hydrogen peroxide is as follows:
O2+2H++2e−→H2O2；
O2+4H++4e−→2H2O；
2H++2e−→H2；
The reaction at the anode 2 is:
2H2O→O2+4H++4e−。
From the above reaction formula, it is known that the electrolysis process not only generates hydrogen peroxide, but also generates other reactions, which affect the purity of the prepared hydrogen peroxide, and the electrolysis process is a four-electron oxygen reduction reaction, so that the concentration of the obtained hydrogen peroxide needs to be increased, and other side reactions need to be avoided.
In the examples of the present invention, the content of c=o and COOH in the cathode 1 obtained by treating the cathode 1 with pre-oxidation and electro-oxidation is greatly increased, which means that carbon atoms on the surface of the cathode 1 are anodized to c=o and COOH. Meanwhile, the surface of the cathode 1 is rich in nitrogen and oxygen functional groups, which are active sites for generating hydrogen peroxide by two electrons. The reaction mechanism is as follows:
G+O2+H++e−→G-OOH；
G-OOH+H++e−→G+H2O2。
wherein G represents an oxygen-containing group or a nitrogen-containing group of a carbon-based material having a surface enriched with nitrogen and oxygen functional groups.
According to some embodiments of the invention, hydrogen peroxide generated by electrochemical action by using the electrolytic cell device for producing hydrogen peroxide can be used as-is, the disinfection and sterilization effect is better than that of manual configuration, the damage to human body is avoided, and toxic residues are avoided after disinfection.
According to some embodiments of the present invention, as further shown in fig. 1-2, the driving assembly 4 includes: the pump 41 is driven for blowing air. And an air duct 42 having one end connected to the driving pump 41 and the other end connected to the cathode 1, and adapted to convey air blown from the driving pump 41 to the cathode 1. The air outlets 421 of the air duct 42 are uniformly distributed on both sides of the bottom of the cathode 1 so that air is delivered to the bottom of the cathode 1 by the driving pump 41 and the air duct 42 to promote the oxygen reduction reaction of the cathode 1.
According to some embodiments of the present invention, the membrane 6 includes a mixed cellulose microfiltration membrane or ion exchange membrane with a pore size of 0.1-1 μm, such as but not limited to 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm. The ion exchange membrane may be, for example, a cation exchange membrane or an anion exchange membrane.
According to some embodiments of the present invention, the cathode 1 may be set to a specification of 10cm×10cm or 20cm×20cm according to the size of the expanded electrolytic cell, and may be sized as needed. The number of the cathodes 1 may be adjusted to 1,2, 3, 4,5, 10 or more sheets as needed, and by providing the number of the cathodes 1 to be different, 1L, 5L or more hydrogen peroxide solutions can be produced.
According to some embodiments of the present invention, the power of the driving pump 41 is 15 to 100W, for example, but not limited to, 15W, 20W, 25W, 30W, 35W, 40W, 45W, 50W, 55W, 60W, 65W, 70W, 75W, 80W, 85W, 90W, 95W or 100W. The air flow rate of the driving pump 41 is 20-100L/min, for example, 20L/min、25L/min、30L/min、35L/min、40L/min、45L/min、50L/min、55L/min、60L/min、65L/min、70L/min、75L/min、80L/min、85L/min、90L/min、95L/min or 100L/min, but not limited thereto. The dc voltage of the power controller 5 is 12 to 96V, for example, but not limited to, 12V, 20V, 30V, 40V, 50V, 60V, 70V, 80V, 90V or 96V. The power supply controller 5 may include, for example, a dc power supply controller, where the dc power supply controller is electrically connected to an external power supply, and is externally connected with 198V/242V ac, and the dc voltage is obtained by transforming the voltage to be 12-96V.
According to some embodiments of the present invention, the current density of the cathode 1 and the anode 2 is 0.5-10 mA/cm 2, for example, but not limited to 0.5mA/cm2、1mA/cm2、2mA/cm2、3mA/cm2、4mA/cm2、5mA/cm2、6mA/cm2、7mA/cm2、8mA/cm2、9mA/cm2 or 10mA/cm 2. The concentration of the generated hydrogen peroxide is 200-1000 mg/L, for example, but not limited to, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L or 1000 mg/L.
According to some embodiments of the invention, after the cathode 1 and the anode 2 are operated for 30-45 min under the condition that the current density is specifically 1-4 mA/cm 2, the concentration of hydrogen peroxide in the electrolytic cell device can reach more than 1000mg/L, so that the current efficiency is more than 95%, the stable performance of generating H 2O2 by electrochemistry is maintained during 1000 cycles, and meanwhile, the service life of the electrode can be effectively prolonged by adopting a cathode and anode alternate reactivation technology. The electrolytic cell device adopts a slot type design, the number of cathodes 1 can be adjusted, the current density is convenient to regulate and control, and the expansibility is strong. Thus, the concentration and yield of hydrogen peroxide can be adjusted to the standards that are suitable for the industry's needs.
According to some embodiments of the invention, a controller is also provided inside the closed container 3 for controlling the turning off and on of the power supply of the electrolytic cell device.
According to an embodiment of a further aspect of the present invention there is provided a use in an electrolytic cell device as described above for achieving water purification, air purification, odour removal, and disinfection cleaning.
According to the embodiment of the invention, the hydrogen peroxide prepared by using the electrolytic cell device can be used as the hydrogen peroxide is produced, no extra salt is needed to be added as electrolyte, the use is convenient, the disinfection and sterilization effect is good, the risk of hydrogen peroxide transportation is avoided, and the transportation cost is reduced. The embodiment of the invention can be applied to the fields of water purification, peculiar smell removal, disinfection and cleaning and the like in families, factories and public places by adjusting the number of the cathodes 1.
The invention is further illustrated by the following comparative examples, figures and related test experiments and the results thereof. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict.
It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto. The chemicals and raw materials used in the examples below were either commercially available or self-made by accepted processing methods.
Example 1:
This example 1 provides a graphite felt material rich in nitrogen and oxygen functional groups, its preparation and characterization, and its preparation method specifically includes the following steps:
The graphite felt was sonicated in ethanol for 30min to remove organic substances attached to the surface, and then washed with ultra pure water to remove residual ethanol and dried for several hours to complete the cleaning process of the graphite felt.
And soaking the cleaned graphite felt in 2M nitric acid for 6 hours at 80 ℃, washing the graphite felt to be neutral by deionized water, and then drying the graphite felt for several hours to obtain the pre-oxidized graphite felt.
The hydrophilic graphite felt is anodized in a 100mL electrolytic tank, tap water or ammonium oxalate is used as a supporting electrolyte, oxidized for 25min under constant current, and the obtained graphite felt rich in nitrogen and oxygen functional groups is thoroughly rinsed with deionized water and dried for several hours.
The original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups were subjected to related tests, the test results of which are as follows.
Fig. 3a is a scanning electron microscope image of the original graphite felt of example 1 of the present invention, and fig. 3b is a scanning electron microscope image of the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention. As can be seen from fig. 3a and 3b, the graphite felt and the graphite felt rich in nitrogen and oxygen functional groups consist of fiber bundles, and the white particles on the fiber surface are slurries that are not completely removed. From the single fiber, the surface of the fiber has ravines with different sizes. The distances between the surface ravines of the graphite felt rich in nitrogen and oxygen functional groups are small, the graphite felt is irregularly distributed, and the overall roughness of the surface is large; compared with the original graphite felt, the surface ravines of the original graphite felt are uniformly distributed along the radial direction, the orientation degree is high, the number is small, and the whole surface is smooth. Generally, the roughened surface provides a larger active area for the electrochemical reaction, accelerating the reaction.
Fig. 4 is a graph comparing raman spectra of the original graphite felt of example 1 of the present invention and a graphite felt rich in nitrogen and oxygen functional groups. Raman spectroscopy is an effective method for accurately characterizing defects and elemental doping in carbon-based materials. As shown in fig. 4, the original graphite felt observed two distinct raman peaks at about 1355cm -1 and 1583cm -1, and the graphite felt enriched in nitrogen and oxygen functional groups observed two distinct raman peaks at about 1346cm -1 and 1575cm -1, representing the D and G peaks, respectively, of the graphite structure. The D peak indicates the degree of surface defects, the G peak is related to the crystalline carbon of graphite, the intensity ratio (I D/IG) of the D peak and the G peak represents the degree of surface defects in the graphite felt, and the larger the I D/IG value is, the lower the graphitization degree is, the more defects are, and the increased defect positions increase the generation of H 2O2 through the two-electron oxygen reduction reaction. The I D/IG values of the original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups are 3.3 and 4.1 respectively, and the ratio of the graphite felt rich in nitrogen and oxygen functional groups is remarkably increased relative to that of the original graphite felt, which shows that the electro-oxidation modification is beneficial to improving the defect degree of the surface of the graphite felt. And the shift of the D and G peaks from the original graphite felt to graphite felt rich in nitrogen and oxygen functional groups to lower wavenumbers suggests a more disordered structure involving carbon-oxygen bonds, indicating the presence of more oxygen-containing functional groups in the defect structure, thereby promoting an increase in oxygen reduction activity.
FIG. 5a is an X-ray photoelectron carbon spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention. FIG. 5b is an X-ray photoelectron spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention. FIG. 5c is an X-ray photoelectron spectrum of the pristine graphite felt and the graphite felt rich in nitrogen and oxygen functional groups of example 1 of the present invention.
The results of XPS full spectrum show that the original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups contain C1s peak, N1s peak, O1s peak. Wherein the raw graphite felt contains up to 82.76% carbon element and 12.08% nitrogen element and only 5.16% oxygen element, indicating that the raw graphite felt surface is highly inert. In the functional group rich in nitrogen and oxygen, the oxygen peak is obviously enhanced, the oxygen element content reaches 17.27%, and the nitrogen element content is 13.22%. This shows that the oxygen content indicated by the graphite felt is greatly increased by progressive oxidation.
As can be seen from fig. 5a, the carbon spectrum curves of the original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups fit to obtain 5 binding energy peaks of 283.6eV, 285.7eV, 286.9eV, 288.1eV and 290.2eV, respectively, corresponding to c= C, C-C, C-OH, c=o and COOH functional groups, respectively. In the carbon spectrum of the original graphite felt, the c=c (83%) and c—o (12.16%) contents account for a large proportion, while the COOH (1.26%) and c=o (3.51%) ratios are small. The content of c=o (18.37%) and COOH (43.19%) in the graphite felt rich in nitrogen and oxygen functional groups was greatly increased, indicating that the pre-oxidation of nitric acid and electrochemical oxidation formed oxygen functional groups (c=o and COOH) on the surface of the graphite felt. As can be seen from fig. 5b, the oxygen spectrum curve fitting of the original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups yields 4 binding energy peaks, 530.1eV, 531.4eV, 532.5eV and 533.9eV, respectively, corresponding to c=o, COOH, C-O-C and H-O-H functional groups, respectively. It can also be seen in the oxygen diagram of the original graphite felt that the content of COOH (86.25%) in the graphite felt rich in nitrogen and oxygen functional groups after pre-oxidation and electro-oxidation is greatly increased compared with the content of COOH (0.86%) in the original graphite felt, wherein carbon-oxygen double bonds and carboxyl groups on the surface of the graphite electrode are active sites for generating hydrogen peroxide by the di-electron oxygen reduction reaction. As can be seen from fig. 5c, the nitrogen spectrum curves of the original graphite felt and the graphite felt rich in nitrogen and oxygen functional groups are fitted to obtain 3 binding energy peaks, 398.3eV, 399.8eV and 401.1eV, respectively, corresponding to pyridine-N, pyrrole-N and graphite-N. It can also be seen in the oxygen profile of the original graphite felt that the pyridine-N (69.96%) and pyrrole-N (24.52%) content of the graphite felt rich in nitrogen and oxygen functional groups was significantly increased over the pyridine-N (15.64%) and pyrrole-N (2.51%) content of the original graphite felt, and the graphite-N (5.72%) content of the graphite felt rich in nitrogen and oxygen functional groups was significantly decreased over the graphite nitrogen (81.86%) content of the original graphite felt, indicating that a relatively large amount of graphite-N was anodized to pyridine-N and pyrrole-N, wherein pyridine-N and pyrrole-N on the surface of the graphite electrode are active sites for the di-electron oxygen reduction reaction to generate hydrogen peroxide.
Example 2:
The present embodiment 2 provides a preparation process of the anode 2 of the electro-oxidized stainless steel mesh, which specifically includes the following steps:
The stainless steel mesh was subjected to ultrasonic treatment in ethanol for 30min to remove organic substances attached to the surface, and then washed with ultrapure water to remove residual ethanol and dried at high temperature for several hours.
The dried stainless steel mesh was anodized in a 100mL electrolytic cell with sodium carbonate as a supporting electrolyte for 60min under constant current.
The original stainless steel mesh and the electro-oxidized stainless steel mesh were subjected to the related test, and the test results thereof are as follows.
FIG. 6a is a scanning electron microscope image of the original stainless steel mesh of example 2 of the present invention, and FIG. 6b is a scanning electron microscope image of the electro-oxidized stainless steel mesh of example 2 of the present invention; as can be seen from fig. 6a and 6b, the surface of the original stainless steel mesh is smoother, and a continuous sheet-like structure film is formed on the surface of the electro-oxidized stainless steel mesh, and the composition of the film mainly comprises iron oxide and hydroxyl oxide, so that the stability of the electro-oxidized stainless steel mesh is ensured.
FIG. 7 is a graph comparing Raman spectra of the original stainless steel mesh and the electro-oxidized stainless steel mesh of example 2 of the present invention. As shown in fig. 7, no distinct raman peaks were observed for the original stainless steel mesh, which suggests that the original stainless steel mesh exists mainly in a metallic state, three distinct raman peaks were observed for the electro-oxidized stainless steel mesh at about 654cm -1、1342cm-1 and 1586cm -1, wherein 654cm -1 and 1342cm -1 could be ascribed to symmetrical stretching vibration and double magnon scattering peaks of α -Fe 2O3 hexacoordinated Fe double-bridged oxygen, a dense oxide film on the electro-oxidized stainless steel mesh surface could be α -Fe 2O3, the degree of densification thereof ensured the stability of the anode 2, 1586cm -1 could be ascribed to the presence of small amounts of γ -FeOOH, and the sheet structure on the electro-oxidized stainless steel mesh surface could be due to the presence of small amounts of γ -FeOOH while containing other trace elements.
Example 3:
This example 3 provides the yield of hydrogen peroxide produced by electrolysis of cathode 1 enriched in nitrogen and oxygen functional groups at different current densities of 30 min.
The electrolysis process comprises the following steps: and adopting an electrolytic cell device shown in fig. 2, directly adopting tap water as electrolyte, carrying out constant current electrolysis for 30min under different current densities, and introducing air with the air quantity of 20-100L/min. The anode 2 is an electro-oxidized stainless steel net, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the air outlets 421 which divide the air duct 42 connected with the driving pump 41 into a plurality of branches are uniformly distributed on two sides of the cathode 1 rich in nitrogen and oxygen functional groups. The apparent area of each cathode 1 rich in nitrogen and oxygen functional groups is 20cm 2, 3 cathodes 1 rich in nitrogen and oxygen functional groups are connected into a circuit, the concentration of hydrogen peroxide in water is sampled and monitored at the water outlet of an electrolytic tank, and the concentration of hydrogen peroxide is measured by a titanium potassium oxalate method.
FIG. 8 is a graph showing the variation in the yield and current efficiency of hydrogen peroxide produced at various current densities in this example 3. As shown in FIG. 8, the cathode 1 rich in nitrogen and oxygen functional groups prepared by the method is electrolyzed for 30min under the constant current condition of 1-3 mA/cm 2, the current efficiency is kept above 95%, but the hydrogen peroxide yield is relatively low.
The electrolysis time was prolonged under a constant current of 3mA/cm 2, and the other electrolysis conditions were the same as above. FIG. 9 is a histogram of the yield of hydrogen peroxide produced at various reaction times in example 3 of the present invention. As shown in FIG. 9, after the time period was prolonged to 45min, the hydrogen peroxide yield was able to reach 1000mg/L, and after the prolonged time period was continued, the hydrogen peroxide concentration was hardly changed, maintained at an equilibrium state, and the current efficiency was gradually decreased. This is because when the hydrogen peroxide concentration reaches a certain concentration, the cathode and anode decompose hydrogen peroxide to produce water and oxygen because the hydrogen peroxide is in an unstable state, so that the hydrogen peroxide concentration is maintained in an equilibrium state after a certain time. The hydrogen peroxide yield was highest at 4mA/cm 2. It is noted that when the current is set to 4mA/cm 2, although the hydrogen peroxide yield is highest, the current efficiency is 85.41%, which means that other side reactions may occur in the graphite cathode rich in nitrogen and oxygen functional groups at the current density, and when the current is set to 1-3 mA/cm 2, although the hydrogen peroxide is produced at a relatively low rate, the current efficiency is high, which means that the graphite cathode undergoes almost only a reaction for generating hydrogen peroxide, almost no other side reactions occur, and the hydrogen peroxide yield increases to a high yield if the electrolysis time is prolonged, so that the graphite cathode is suitable for use in a relatively closed and narrow space environment such as a household.
Example 4:
This example 4 provides the yield of hydrogen peroxide produced by electrolysis of cathode 1 enriched in nitrogen and oxygen functional groups under different electrolyte conditions of 30min.
The electrolysis process comprises the following steps: and (3) continuing to electrolyze for 30min under the constant current condition of 4mA/cm 2 by adopting the electrolytic cell device shown in the figure 2, wherein the air quantity is 20-100L/min. The anode 2 is an electrooxidation stainless steel net, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the structure of the electrolytic cell device is the same as that of the embodiment 3, and the details are omitted here. The concentration of hydrogen peroxide in water is monitored by sampling at the water outlet of the electrolytic tank, and the concentration of hydrogen peroxide is measured by a titanium potassium oxalate method.
Fig. 10 is a graph showing the variation in hydrogen peroxide production and current efficiency generated when different electrolytes were used in this example 4. As can be seen from fig. 10, the cathode 1 rich in nitrogen and oxygen functional groups is suitable for tap water, sodium carbonate and acid sodium sulfate electrolyte, and can maintain nearly the same hydrogen peroxide yield and current efficiency as those of sodium carbonate and acid sodium sulfate in tap water, so tap water is directly used as electrolyte, no additional salt is needed to be added as electrolyte, the electrolytic process is simplified, and the use is convenient.
Example 5:
This example 5 provides a process for preparing hydrogen peroxide by electrolysis of cathode 1 rich in nitrogen and oxygen functional groups under different membrane conditions for 30min.
The electrolysis process comprises the following steps: and (3) continuing to electrolyze for 30min under the constant current condition of 4mA/cm 2 by adopting the electrolytic cell device shown in the figure 2, and introducing air with the air quantity of 20-100L/min. The anode 2 is an electrooxidation stainless steel net, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the structure of the electrolytic cell device is the same as that of the embodiment 3, and the details are omitted here. The concentration of hydrogen peroxide in water is monitored by sampling at the water outlet of the electrolytic tank, and the concentration of hydrogen peroxide is measured by a titanium potassium oxalate method.
FIG. 11 is a graph showing the variation in hydrogen peroxide production and current efficiency produced when using different membrane types in example 5 of the present invention. As shown in fig. 11, when a cation exchange membrane (nafion membrane) is used, the yield and current efficiency of hydrogen peroxide are highest; when using microfiltration membranes of different pore sizes, the hydrogen peroxide yield and current efficiency are slightly reduced, so different types of membranes can be selected according to different needs.
Example 6:
This example 6 provides the yield of hydrogen peroxide produced after 30 minutes of electrolysis of the different cathodes 1 prepared according to the preparation method in example 1.
The electrolysis process comprises the following steps: and (3) adopting an electrolytic cell device shown in the figure 2, and electrolyzing for 30min under the constant current condition of 4mA/cm 2, wherein the air quantity is 20-100L/min. The anode 2 is an electro-oxidized stainless steel net, and the cathode 1 is made of different carbon-based materials. The gas-guide tube 42 connected to the driving pump 41 is divided into a plurality of branched gas outlets 421 uniformly distributed on both sides of the cathode 1 of different carbon bases. The apparent area of each of the different carbon-based cathodes 1 was 20cm 2, and a total of 3 different carbon-based cathodes 1 were connected to a circuit. The concentration of hydrogen peroxide in water is monitored by sampling at the water outlet of the electrolytic tank, and the concentration of hydrogen peroxide is measured by a titanium potassium oxalate method.
FIG. 12 is a histogram of hydrogen peroxide yields generated in example 6 of the present invention when different cathode materials are used. As shown in fig. 12, the unmodified carbon-based material has little selectivity for hydrogen peroxide generation, and when the modified different carbon-based materials are used to prepare the cathode 1 under the same conditions as described above to generate hydrogen peroxide, the preparation method is applicable to most carbon-based materials, and the graphite felt material shows the highest hydrogen peroxide yield.
Example 7:
this example 7 provides electrode stability for a cathode 1 of graphite rich in nitrogen and oxygen functional groups and an anode 2 of an electro-oxidized stainless steel mesh.
The electrolysis process comprises the following steps: and continuing to adopt the electrolytic cell device shown in the figure 2, electrolyzing under the constant current condition of 4mA/cm 2, and introducing air with the air quantity of 20-100L/min. The anode 2 is an electrooxidized stainless steel net, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the structure of the electrolytic cell device is the same as that of the embodiment 3, and the details are not repeated here. The concentration of hydrogen peroxide in water is monitored by sampling at the water outlet of the electrolytic tank, and the concentration of hydrogen peroxide is measured by a titanium potassium oxalate method.
FIG. 13 is a histogram of change in electrode stability test for example 7 of the present invention. As shown in FIG. 13, after 500 cycles of the cathode and anode of the electrolytic cell device, the hydrogen peroxide yield was slightly reduced, at this time, the cathode 1 and anode 2 of the electrolytic cell device were inverted, i.e., the graphite felt electrode rich in nitrogen and oxygen functional groups was the anode 2, the oxidized graphite electrode was reoxidized by the electro-oxidized stainless steel mesh as the cathode 1 for 180 minutes, the oxidation current was 60mA, and then the cathode and anode of the electrolytic cell device were inverted to enter the working state. The electrode in the electrolytic cell device can achieve larger hydrogen peroxide yield, and the stability of the electrode can reach 1000 cycles.
Example 8:
This example 8 provides a cathode 1 of graphite rich in nitrogen and oxygen functional groups and an anode 2 of an electro-oxidized stainless steel mesh, and the sterilizing effect of the hydrogen peroxide sterilizing solution generated after electrolysis for 30min was tested in an electrolytic cell apparatus as shown in fig. 2.
The electrolysis process comprises the following steps: and (3) continuing to electrolyze by adopting the electrolytic cell device shown in the figure 2 under the constant current condition of 4mA/cm 2, and introducing air with the air quantity of 20-100L/min. The anode 2 is an electrooxidized stainless steel net, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the structure of the electrolytic cell device is the same as that of the embodiment 3, and the details are not repeated here. Sampling at the water outlet of the electrolytic tank for sterilization experiment.
The sterilizing effect inspection method of the sterilizing agent laboratory is based on GB/T38502-2020. Gram negative E.coli (E.coil) and gram positive Staphylococcus aureus (S.aureus) were used to evaluate the sterilizing effect of the sterilizing solution produced by the cathode 1 of the graphite oxide felt of the electrolytic cell device in example 8.
The experimental process comprises the following steps: 100 microliters of solution was added to the 48-well plate followed by a sterile phosphate buffer containing 200 microliters of bacterial suspension (10 4 CFU/mL). They were then incubated in a thermostat at 37℃for 6 hours, using bacterial medium without solution as a control. Transferring the co-culture into 100 mu L of solid agar medium, incubating for 16-24 h at 37 ℃, counting, photographing and recording colony forming units on agar plates, and repeating each experiment three times.
Fig. 14 is a schematic view showing the effect of hydrogen peroxide sterilization produced in example 8. As shown in fig. 14, the disinfectant generated by the electrolytic cell device almost kills 100% of bacteria, and can meet the requirements of sterilization and disinfection.
Comparative example 1
This comparative example provides the sterilizing effect of manually dispensing hydrogen peroxide sterilizing solution at the same concentration as in example 8.
The sterilizing effect inspection method of the sterilizing agent laboratory is based on GB/T38502-2020. Gram-negative E.coli (E.coil) and gram-positive Staphylococcus aureus (S.aureus) were used to evaluate the bactericidal effect of the manually formulated hydrogen peroxide disinfectant.
The experimental process comprises the following steps: 100. Mu.L of the solution was added to a 48-well plate, followed by 200. Mu.L of sterile phosphate buffer containing bacterial suspension (10 4 CFU/mL). They were then incubated in a thermostat at 37℃for 6 hours, using bacterial medium without solution as a control. Transferring the co-culture into 100 mu L of solid agar medium, incubating for 16-24 h at 37 ℃, counting, photographing and recording colony forming units on agar plates, and repeating each experiment three times.
Fig. 15 is a schematic view showing the sterilizing effect of hydrogen peroxide manually formulated in comparative example 1 of the present invention. As shown in fig. 15, the sterilizing effect of the hydrogen peroxide sterilizing solution prepared manually with the same concentration is obviously less than that of the hydrogen peroxide sterilizing solution generated in situ in example 8, which indicates that the hydrogen peroxide generated in situ by electrochemistry has higher sterilizing activity.
In summary, referring to fig. 1-2, the present invention provides an electrode assembly of an electrolytic cell, an electrolytic cell apparatus for producing hydrogen peroxide and applications thereof. When the electrolytic cell device is used, the driving pump 41 is started through the power supply controller 5, at this time, the driving pump 41 works to transmit oxygen in air to the cathode 1 of the graphite rich in nitrogen and oxygen functional groups, then the direct current power supply is started through the power supply controller 5, as shown in the embodiment 3, the power supply controller 5 can set a plurality of gears, namely different current densities, according to the requirements, if the electrolytic cell device is used in a relatively closed and narrow space of a household, the electrolytic cell device can be set into a small gear, namely 1-3 mA/cm 2, and the electrolytic time can be prolonged properly; if the device is used in a factory in a space ventilation environment, a higher gear can be set. The electrolysis time is relatively short, and generally, the hydrogen peroxide disinfectant with strong sterilization capability can be prepared within 30 minutes, and if the hydrogen peroxide disinfectant with higher concentration is needed, the longer electrolysis time can be set according to the needs. When the setting is completed, the electrolytic cell device for producing hydrogen peroxide starts to work, and when the setting time is reached, the power supply controller 5 automatically turns off the direct current power supply and drives the power switch of the pump 41, and the hydrogen peroxide disinfectant is manufactured.
The electrical components appearing herein are all electrically connected with the master controller and the power supply, the master controller can be a conventional known device for controlling a computer and the like, and the prior art of power connection is not described in detail herein.
From the electrolysis cost and the materials used, the raw materials are tap water, the anode 2 is an electro-oxidized stainless steel mesh, the cathode 1 is a graphite felt rich in nitrogen and oxygen functional groups, and the raw materials are cheap and easy to obtain. Therefore, the electrode assembly of the electrolytic cell and the electrolytic cell device containing the same for producing hydrogen peroxide are simple in equipment, low in electricity consumption cost, high in stability and good in disinfection and sterilization effect, and have feasibility of being applied to offices, hotels, families, restaurants, factories and other places.
It should be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (8)
1. A method for producing hydrogen peroxide using tap water as an electrolyte, characterized by using an electrolytic cell device for producing hydrogen peroxide, the electrolytic cell device comprising:
a closed container for accommodating an electrolyte;
an electrode assembly disposed within the sealed container;
a drive assembly in communication with the closed container adapted to deliver air to the cathode of the electrode assembly such that oxygen in the air is reduced to hydrogen peroxide under the electrocatalytic effect of the cathode;
the power supply controller is electrically connected with the electrode assembly and is suitable for providing electron flow for the electrode assembly;
a separator disposed between the cathode and the anode of the electrode assembly for preventing hydrogen peroxide from being transferred to the anode so that the hydrogen peroxide is decomposed;
Wherein the electrode assembly includes: a cathode and an anode; the cathode comprises a carbon-based material rich in nitrogen and oxygen functional groups, providing an electrocatalytic effect for the reduction of oxygen to hydrogen peroxide;
wherein the carbon-based material rich in nitrogen and oxygen functional groups is prepared by progressive oxidation:
immersing the first carbon-based material in a nitric acid solution, and performing pre-oxidation treatment for 3-9 hours at 50-100 ℃ to obtain a hydrophilic second carbon-based material;
performing electrooxidation treatment on the second carbon-based material for 10-30 min to convert graphite nitrogen in the second carbon-based material into pyridine nitrogen and pyrrole nitrogen and generate carboxyl and carbon-oxygen double bonds, wherein the first carbon-based material is graphite felt, and the electrolyte of the electrooxidation treatment comprises tap water, or the electrolyte of the electrooxidation treatment comprises a solution containing acid, alkali or salt;
The electrolyte of the electrolytic cell is tap water; wherein, the current density of the cathode and the anode is 1-4 mA/cm 2, the electrolysis time is 30-45 min, and the concentration of the produced hydrogen peroxide can reach more than 1000 mg/L;
The anode is made of stainless steel material subjected to anodic oxidation activation treatment, the surface of the anode is provided with metal oxide and metal oxyhydroxide, the metal oxide is alpha-Fe 2O3, and the metal oxyhydroxide is gamma-FeOOH;
In the carbon-based material rich in nitrogen and oxygen functional groups, the content of oxygen element is 17.27%, and the content of nitrogen element is 13.22%.
2. The method of claim 1, wherein the first carbon-based material is subjected to ultrasonic, water washing, and drying treatments in sequence before being immersed in the nitric acid solution.
3. The method of claim 1, wherein the cathode and anode are configured to be reactivated by alternating cathodes and anodes.
4. The method according to claim 1, wherein the electrode assembly comprises a plurality of the cathodes and 2 anodes, the 2 anodes being arranged in parallel at intervals, the plurality of the cathodes being respectively arranged vertically between the 2 anodes and being arranged in parallel at intervals along the extending direction of the anodes;
The anode is constructed in a mesh structure, and the mesh number of the mesh structure is 1000-3500.
5. The method of claim 1, wherein the drive assembly comprises:
a driving pump for blowing air;
And one end of the air duct is communicated with the driving pump, and the other end of the air duct is connected with the cathode and is suitable for conveying air blown by the driving pump to the bottom of the cathode.
6. The method according to claim 1, wherein the membrane comprises a mixed cellulose microfiltration membrane or an ion exchange membrane having a pore size of 0.1-1 μm.
7. The method of claim 5, wherein the power of the driving pump is 15-100 w, and the air flow rate of the driving pump is 20-100 l/min;
the direct-current voltage of the power supply controller is 12-96V.
8. Use of the method according to any one of claims 1 to 7 for water purification, air purification, odor removal and disinfection cleaning.
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