CN114054032A - Preparation method and application of strontium perovskite catalytic cathode - Google Patents
Preparation method and application of strontium perovskite catalytic cathode Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 63
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 19
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010936 titanium Substances 0.000 claims abstract description 57
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 23
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010865 sewage Substances 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- PKIDNTKRVKSLDB-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PKIDNTKRVKSLDB-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 229910013722 M(NO3)2 Inorganic materials 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 5
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 abstract description 13
- 239000010949 copper Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MJEHGIOAOSQVCA-UHFFFAOYSA-N [Ni].[Sr] Chemical compound [Ni].[Sr] MJEHGIOAOSQVCA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002400 SrCoO3−δ Inorganic materials 0.000 description 1
- 229910002411 SrFeO3−δ Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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Abstract
The invention discloses a preparation method and application of a strontium perovskite catalytic cathode, which comprises a porous titanium sheet electrode and a catalytic layer, wherein the catalytic layer is a perovskite catalytic layer generated in situ on the porous titanium sheet electrode, and the catalytic layer is SrMO3Wherein M is one or more of Cu, Fe and Co, and the method comprises the following steps: s1: sr (NO)3)2、M(NO3)2·6H2Mixing O with sodium citrate monohydrate and ethylene glycol, and evaporating water to dryness to obtain gel; s2: pretreating the porous titanium sheet electrode; s3: soaking the pretreated porous titanium sheet electrode in gel until no bubbles are generated; s4: drying and calcining the soaked porous titanium sheet electrodeGenerating a catalyst layer on the surface of the porous titanium sheet electrode; s5: repeating the soaking-drying-calcining process to obtain SrMO3Catalytic electrode, SrMO prepared by the invention3The catalytic cathode has simple preparation method and high ammonia nitrogen selectivity, can be used for sewage treatment, converts nitrate nitrogen into ammonia nitrogen, and lays a foundation for the resource utilization of nitrate sewage.
Description
Technical Field
The invention relates to the technical field of electrochemical sewage treatment recycling, in particular to a preparation method and application of a strontium perovskite catalytic cathode.
Background
Due to the large use of agricultural nitrogen fertilizers and the rapid development of industries such as metal processing and the like, the pollution of nitrate nitrogen in water bodies is getting more and more serious. With the proposition of the concepts of changing waste into valuable and carbon neutralization, the development of a sewage treatment and recycling technology for effectively removing nitrate nitrogen in sewage and simultaneously converting the nitrate nitrogen into ammonia nitrogen (an important agricultural nitrogen fertilizer) becomes a research hotspot.
At present, commonly used treatment methods for nitrate nitrogen in sewage include ion exchange, reverse osmosis, membrane separation, biological denitrification and the like. Among them, the technologies of ion exchange, reverse osmosis, membrane separation, etc. are to separate nitrate from water, and the problem of producing a large amount of brine for further treatment is faced. The common biological treatment technology also has the defects of complex device, high requirement on environmental conditions, low reaction efficiency and the like. Meanwhile, the above technology only removes the nitrate in the sewage, but does not convert the nitrate into valuable products such as ammonia nitrogen and the like, and the resource utilization cannot be realized. The electro-catalytic reduction technology can reduce and remove nitrate nitrogen and convert the nitrate nitrogen into ammonia nitrogen, has high reaction rate, high equipment integration level, simple and convenient operation and environmental protection, and is a nitrate sewage treatment recycling technology with great prospect.
The electrode material determines the removal rate of nitrate and the selectivity of ammonia nitrogen by the electro-catalytic reduction technology, so that the preparation of the high-performance cathode material is the key of the electro-chemical catalytic reduction technology. At present, common cathode materials are concentrated on a series of noble metals such as palladium, ruthenium, platinum and the like, transition metals such as copper, iron, cobalt and the like and oxides thereof, and the problems of high cost, insufficient stability and the like are often existed. Perovskite (ABO) in recent years3Structure) material is rich in reserves, low in price and crystallineThe catalyst has the characteristics of flexible and changeable body and electronic structure, and the like, and is widely applied to the research of electrocatalytic hydrogen evolution as a novel non-noble metal catalyst. Based on the reaction principle that electrochemical nitrate catalytic reduction is similar to electrochemical hydrogen evolution, the perovskite material can be used as a cheap and stable catalyst to realize efficient nitrogen recycling of the electrochemical technology.
Disclosure of Invention
The invention aims to provide a preparation method and application of a strontium perovskite catalytic cathode, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the strontium perovskite catalytic cathode comprises a porous titanium sheet electrode and a catalytic layer, wherein the catalytic layer is a perovskite catalytic layer generated in situ on the porous titanium sheet electrode.
Further, the catalytic layer is SrMO3Wherein M is one or more of Cu, Fe and Co.
Further, the method comprises the following steps:
s1 preparation of Sr (NO)3)2、M(NO3)2·6H2Mixing O with sodium citrate monohydrate to prepare gel, wherein M is one or more of Cu, Fe and Co;
s2: pretreating the porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in gel, drying and calcining to generate a catalyst layer on the surface;
s4: repeating the soaking-drying-calcining process to obtain SrMO3A catalytic electrode.
Further, the method comprises the following steps:
s1: sr (NO)3)2、M(NO3)2·6H2Mixing O and sodium citrate monohydrate uniformly, adding ethylene glycol, mixing uniformly, keeping the temperature at 80-90 ℃ for 10-12h, and evaporating water to dryness to obtain gel;
s2: soaking the porous titanium sheet electrode in an oxalic acid solution at the temperature of 100-110 ℃, and carrying out acid cleaning for 1-3h, and then carrying out ultrasonic treatment until the solution becomes clear, namely the pretreated porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in the gel for 5-10min until no bubbles are generated;
s4: drying the soaked porous titanium sheet electrode at 80-90 ℃ for 20-30min, then calcining at 700 ℃ for 3-4h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s5: repeating the soaking-drying-calcining process to obtain SrMO3A catalytic electrode.
Further, the SrMO3The catalytic electrode also comprises the following preparation method: taking a pretreated porous titanium sheet electrode as a cathode and a platinum sheet electrode as an anode, placing the electrodes in an electrodeposition solution at 40-60 ℃, electrodepositing for 20-30min, drying, and then soaking into gel, wherein the electrodeposition solution is a mixed solution of graphene oxide and sodium sulfate.
Further, the preparation method of the modified graphene oxide comprises the following steps: uniformly mixing graphene oxide and water, carrying out ultrasonic reaction for 1-1.5h, introducing nitrogen, reacting for 0.5-1h, adding a ferrous sulfate solution, reacting for 8-12h, slowly dropwise adding sodium borohydride, continuously reacting for 3-6h, adding nano zinc oxide, reacting for 1-2h, centrifuging, and washing for 4-6 times with water to obtain the modified graphene oxide.
Further, the preparation method of the nano zinc oxide comprises the following steps: uniformly mixing zinc nitrate and water, adding sodium carboxymethyl cellulose and sodium hydroxide solution, reacting for 1-2h, heating to 120 ℃ for further reaction for 12-15h, washing with ethanol and water for 3-5 times, centrifuging for 5-10min, and drying to obtain the nano zinc oxide.
Further, the SrMO3The catalytic electrode is applied to sewage treatment and can catalyze and reduce nitrate in sewage into ammonia nitrogen.
Further, the SrMO3The catalytic electrode is positioned in the middle of an electrochemical system and serves as a working cathode, and the two reticular ruthenium-iridium electrodes serve as anodes.
Further, the distance between the cathode and the anode is 1-3cm, and the current density range is 1-6 mA/cm2。
Further, the materials required by the modified graphene oxide comprise, by weight: 2-8 parts of graphene oxide, 70-80 parts of water, 10-20 parts of ferrous sulfate, 20-30 parts of sodium borohydride and 2-8 parts of nano zinc oxide.
Further, the required materials of the nano zinc oxide comprise, by weight: 14-20 parts of zinc nitrate, 80-100 parts of water, 1-5 parts of sodium carboxymethyl cellulose and 10-15 parts of sodium hydroxide.
Further, the mass ratio of the modified graphene oxide to the sodium sulfate is 1: 8.
compared with the prior art, the invention has the following beneficial effects: (1) the calcination in the preparation process of the strontium perovskite catalyst layer is carried out in the air atmosphere at 700 ℃, the retention time is 3h, the heating rate is 5 ℃/min, the calcination temperature and time can influence the crystal form and the surface composition of the in-situ growth of the strontium nickel perovskite, and the crystallinity of the strontium nickel perovskite can be influenced when the calcination temperature is too high or too low; the strontium perovskite catalytic cathode is prepared for the first time, has wide raw material sources and low price, is simple to operate, has low production cost and is suitable for industrial production; the strontium perovskite catalytic cathode electrochemical system provided by the invention has stable operation efficiency and low metal ion precipitation concentration, and cannot cause subsequent pollution.
(2) The porous titanium sheet electrode is electrodeposited in a modified graphene oxide mixed solution, nitrate nitrogen in sewage is adsorbed on the surface of graphene oxide, then an oxidation-reduction reaction is carried out on the surface, the nitrate nitrogen is converted into ammonia nitrogen, ferrous iron is reduced into nano zero-valent iron by using sodium borohydride, the nano zero-valent iron is loaded on the surface of the graphene oxide, the phenomenon that the nano iron is aggregated can be avoided, the dispersity is improved, active sites on the surface of the nano iron are increased, micro-electrolysis is formed between the nano iron and the graphene oxide, and the electric conductivity of the graphene is favorable for transferring electrons in the reaction,simultaneously, active hydrogen can be generated in the oxidation-reduction reaction, the reducibility of the nano-iron is further improved, and the SrMO is enhanced3The catalytic electrode has the conversion efficiency of converting nitrate nitrogen into ammonia nitrogen, and meanwhile, the graphene oxide can reduce the recombination efficiency of electron-hole pairs on the surface of zinc oxide, so that the content of ammonia nitrogen in sewage can be reduced, reaction products are ammonia gas and nitrate nitrogen, the nitrate nitrogen can be converted into ammonia nitrogen, and the subsequent recovery of the ammonia nitrogen is facilitated.
(3) The electrochemical system of the invention is a double cathode, SrMO3The catalytic electrode is positioned in the middle and used as a working cathode, the two reticular ruthenium iridium electrodes are used as anodes and used as counter electrodes, the area of the anodes is increased to avoid the influence of the anodes on the reaction, ammonia nitrogen generated by reduction is not oxidized in the anodes in a large amount, the ammonia nitrogen is favorably accumulated and recovered, and meanwhile, the current density is controlled, and the oxidation of a catalytic layer is avoided.
(4) The electrocatalytic reduction technology provided by the invention is suitable for removing and converting nitrate nitrogen in natural water and sewage, and meanwhile, the reaction system finally becomes alkaline (pH value is 10), so that the electrocatalytic reduction technology is beneficial to subsequent recovery technologies of stripping of ammonia nitrogen resources, membrane absorption and the like, and has the advantages of high conversion efficiency, high speed and no pollution.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic representation of a copper strontiate catalytic cathode prepared in example 1;
FIG. 2 is the XRD pattern of the copper strontiate catalytic cathode prepared in example 1;
FIG. 3 is an SEM image of a copper strontiate catalytic cathode prepared in example 1;
FIG. 4 is a mapping diagram of a copper strontiate catalytic cathode prepared in example 1;
FIG. 5 is a diagram of an apparatus for electrochemical removal of nitrate using a copper strontiate catalytic cathode;
FIG. 6 is a graph showing the effect of removing nitrate in example 1 and comparative example 1;
FIG. 7 is a graph showing the effect of nitrate conversion to ammonia nitrogen in example 1 and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: the method comprises the following steps:
s1: adding Cu (NO)3)2·6H2O and Sr (NO)3)2Dissolving in 25ml water at a metal ion ratio of 1:1, wherein Cu (NO)3)2·6H2O concentration of 0.25mol/L, Sr (NO)3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of glycol solution, slowly stirring, keeping the temperature at 80 ℃ for 10 hours, and evaporating to remove water to obtain gel;
s2: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at 100 ℃, carrying out acid cleaning for 1h, and carrying out ultrasonic treatment until the solution becomes clear, thus obtaining the pretreated porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in the gel for 5min until no bubbles are generated;
s4: drying the soaked porous titanium sheet electrode at 80 ℃ for 20min, then calcining at 700 ℃ for 3h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s5: the soaking-drying-calcining process is repeated for 5 times to obtain SrCuO3-δA catalytic electrode.
Example 2: the method comprises the following steps:
s1: mixing Fe (NO)3)2And Sr (NO)3)2Dissolving in 25ml water at metal ion ratio of 1:1, wherein Fe (NO)3)2Sr (NO) with a concentration of 0.25mol/L3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of glycol solution, slowly stirring, keeping the temperature at 80 ℃ for 10 hours, and evaporating to remove water to obtain gel;
s2: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at 100 ℃, carrying out acid cleaning for 1h, and carrying out ultrasonic treatment until the solution becomes clear, thus obtaining the pretreated porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in the gel for 5min until no bubbles are generated;
s4: drying the soaked porous titanium sheet electrode at 80 ℃ for 20min, then calcining at 700 ℃ for 3h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s5: repeating the soaking, drying and calcining processes for 5 times to obtain SrFeO3-δA catalytic electrode.
Example 3: comprises the following steps
S1: mixing Co (NO)3)2·6H2O and Sr (NO)3)2Dissolving in 25ml water at a metal ion ratio of 1:1, wherein Co (NO)3)2·6H2O concentration of 0.25mol/L, Sr (NO)3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of glycol solution, slowly stirring, keeping the temperature at 80 ℃ for 10 hours, and evaporating to remove water to obtain gel;
s2: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at 100 ℃, carrying out acid cleaning for 1h, and carrying out ultrasonic treatment until the solution becomes clear, thus obtaining the pretreated porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in the gel for 5min until no bubbles are generated;
s4: drying the soaked porous titanium sheet electrode at 80 ℃ for 20min, then calcining at 700 ℃ for 3h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s5: repeating the soaking-drying-calcining process for 5 times to obtain SrCoO3-δA catalytic electrode.
Example 4: the method comprises the following steps:
s1: uniformly mixing 14 parts of zinc nitrate and 80 parts of water, adding 1 part of sodium carboxymethyl cellulose and 10 parts of sodium hydroxide solution, reacting for 1 hour, heating to 100 ℃, continuing to react for 12 hours, washing with ethanol and water for 3 times, centrifuging for 5min, and drying to obtain nano zinc oxide;
s2: uniformly mixing 7 parts of graphene oxide and 70 parts of water, carrying out ultrasonic reaction for 1 hour, introducing nitrogen, reacting for 0.5 hour, adding 10 parts of 0.05mol/L ferrous sulfate solution, reacting for 8-12 hours, slowly dropwise adding 20 parts of 0.2mol/L sodium borohydride, continuously reacting for 3 hours, adding 7 parts of nano zinc oxide, reacting for 1 hour, centrifuging, and washing for 4 times with water to obtain modified graphene oxide;
s3: adding Cu (NO)3)2·6H2O and Sr (NO)3)2Dissolving in 25ml water at a metal ion ratio of 1:1, wherein Cu (NO)3)2·6H2O concentration of 0.25mol/L, Sr (NO)3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of ethylene glycol solution, slowly stirring, keeping the temperature at 80 ℃ for 10 hours, and evaporating to remove water to obtain gel;
s4: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at 100 ℃, carrying out acid cleaning for 1h, and carrying out ultrasonic treatment until the solution becomes clear, thus obtaining the pretreated porous titanium sheet electrode;
s5: taking a pretreated porous titanium sheet electrode as a cathode and a platinum sheet electrode as an anode, placing the pretreated porous titanium sheet electrode in a mixed solution of modified graphene oxide and 0.05mol/L sodium sulfate at 40 ℃, carrying out electrodeposition for 20min at a current intensity of 10mA, drying, and then soaking in gel for 5min until no bubbles are generated;
s6: drying the soaked porous titanium sheet electrode at 80 ℃ for 20min, then calcining at 700 ℃ for 3.5h, heating at the speed of 5 ℃/min, and generating a catalyst layer on the surface of the porous titanium sheet electrode;
s7: heavy loadThe process of soaking, drying and calcining is carried out for 5 times again to obtain SrCuO3-δA catalytic electrode.
The mass ratio of the modified graphene oxide to the sodium sulfate is 1: 8.
example 5: the method comprises the following steps:
s1: uniformly mixing 16 parts of zinc nitrate and 83 parts of water, adding 3 parts of sodium carboxymethyl cellulose and 12 parts of sodium hydroxide solution, reacting for 1.3h, heating to 105 ℃, continuing to react for 13h, washing with ethanol and water for 4 times, centrifuging for 7min, and drying to obtain nano zinc oxide;
s2: uniformly mixing 3 parts of graphene oxide and 72 parts of water, carrying out ultrasonic reaction for 1.3h, introducing nitrogen, reacting for 0.7h, adding 13 parts of 0.05mol/L ferrous sulfate solution, reacting for 9h, slowly dropwise adding 23 parts of 0.2mol/L sodium borohydride, continuously reacting for 4h, adding 3 parts of nano zinc oxide, reacting for 1.1h, centrifuging, and washing with water for 4 times to obtain modified graphene oxide;
s3: adding Cu (NO)3)2·6H2O and Sr (NO)3)2Dissolving in 25ml water at a metal ion ratio of 1:1, wherein Cu (NO)3)2·6H2O concentration of 0.25mol/L, Sr (NO)3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of ethylene glycol solution, slowly stirring, keeping the temperature at 90 ℃ for 11 hours, and evaporating to remove water to obtain gel;
s4: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at 105 ℃, carrying out acid washing for 2 hours, and carrying out ultrasonic treatment until the solution becomes clear, thus obtaining the pretreated porous titanium sheet electrode;
s5, placing the pretreated porous titanium sheet electrode as a cathode and the platinum sheet electrode as an anode in a mixed solution of modified graphene oxide and 0.05mol/L sodium sulfate at 42 ℃, carrying out electrodeposition for 22min with the current intensity of 10mA, drying, and soaking in gel for 8min until no bubbles are generated;
s6: drying the soaked porous titanium sheet electrode at 90 ℃ for 30min, then calcining at 700 ℃ for 4h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s7: the soaking-drying-calcining process is repeated for 5 times to obtain SrCuO3-δA catalytic electrode.
The mass ratio of the modified graphene oxide to the sodium sulfate is 1: 8.
example 6: the method comprises the following steps:
s1: uniformly mixing 16 parts of zinc nitrate and water, adding 5 parts of sodium carboxymethyl cellulose and 13 parts of sodium hydroxide solution, reacting for 1.6 hours, heating to 115 ℃, continuing to react for 14 hours, washing with ethanol and water for 4 times, centrifuging for 8min, and drying to obtain nano zinc oxide;
s2: uniformly mixing 4 parts of graphene oxide and 75 parts of water, carrying out ultrasonic reaction for 1.3h, introducing nitrogen, reacting for 0.8h, adding 15 parts of 0.05mol/L ferrous sulfate solution, reacting for 10h, slowly dropwise adding 25 parts of 0.2mol/L sodium borohydride, continuously reacting for 5h, adding 4 parts of nano zinc oxide, reacting for 1.3h, centrifuging, and washing for 5 times with water to obtain modified graphene oxide;
s3: adding Cu (NO)3)2·6H2O and Sr (NO)3)2Dissolving in 25ml water at a metal ion ratio of 1:1, wherein Cu (NO)3)2·6H2O concentration of 0.25mol/L, Sr (NO)3)2The concentration is 0.25 mol/L; dissolving 6.02g of sodium citrate monohydrate in 25mL of water, mixing the two solutions to obtain 50mL of mixed solution, slowly adding 6.9mL of ethylene glycol solution, slowly stirring, keeping the temperature at 85 ℃ for 11 hours, and evaporating to remove water to obtain gel;
s4: cutting the porous titanium sheet electrode into 3cm by 2mm, soaking the electrode in 10% oxalic acid solution at the temperature of 100-;
s5: taking a pretreated porous titanium sheet electrode as a cathode and a platinum sheet electrode as an anode, placing the pretreated porous titanium sheet electrode in a mixed solution of modified graphene oxide and 0.05mol/L sodium sulfate at 45 ℃, carrying out electrodeposition for 25min under the current intensity of 10mA, drying, and then soaking in gel for 9min until no bubbles are generated;
s6: drying the soaked porous titanium sheet electrode at 80 ℃ for 20min, then calcining at 700 ℃ for 3h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s7: the soaking-drying-calcining process is repeated for 5 times to obtain SrCuO3-δA catalytic electrode.
The mass ratio of the modified graphene oxide to the sodium sulfate is 1: 8.
comparative example
Comparative example 1: in contrast to example 1, the cathode of the electrochemical system was made of SrCuO3-δThe catalytic electrode is a pure copper sheet electrode with the same size, and the anode is two ruthenium iridium mesh electrodes with the same size.
Comparative example 2: compared with the embodiment 4, the preparation method is the same as the invention without adding the nano zinc oxide in the raw materials.
Experimental data
An electrocatalytic reduction system was constructed using the catalytic electrodes prepared in examples 1 to 6, comparative examples 1 and 2 as cathodes and two ruthenium iridium mesh electrodes of the same size as anodes, and 70ml of simulated wastewater was added, wherein 50mM sodium sulfate was used as an electrolyte, 50mg/L nitrate was used as a target pollutant, and the current density of the system was 4.24mA/cm2The reaction was carried out for 120min and the results are shown in the following table.
Table 1 test results of various properties of catalytic electrodes of examples 1 to 3 and comparative example 1
Table 2 results of measuring properties of catalytic electrodes of examples 4 to 6 and comparative example 2
And (4) conclusion: the catalytic electrode prepared by the method has the advantages of high conversion efficiency, high speed and no pollution.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, 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.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A strontium perovskite catalytic cathode is characterized in that: the catalyst layer is a perovskite catalyst layer generated in situ on the porous titanium sheet electrode.
2. The strontium perovskite catalytic cathode of claim 1, wherein: the catalyst layer is SrMO3Wherein M is one or more of Cu, Fe and Co.
3. A preparation method of a strontium perovskite catalytic cathode is characterized by comprising the following steps: the method comprises the following steps:
s1 preparation of Sr (NO)3)2、M(NO3)2·6H2O and lemon monohydrateMixing sodium salts to obtain gel, wherein M is one or more of Cu, Fe and Co;
s2: pretreating the porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in gel, drying and calcining to generate a catalyst layer on the surface;
s4: repeating the soaking-drying-calcining process to obtain SrMO3A catalytic electrode.
4. The method for preparing a strontium perovskite catalytic cathode according to claim 3, wherein the method comprises the following steps: the method comprises the following steps:
s1: sr (NO)3)2、M(NO3)2·6H2Mixing O and sodium citrate monohydrate uniformly, adding ethylene glycol, mixing uniformly, keeping the temperature at 80-90 ℃ for 10-12h, and evaporating water to dryness to obtain gel;
s2: soaking the porous titanium sheet electrode in an oxalic acid solution at the temperature of 100-110 ℃, and carrying out acid cleaning for 1-3h, and then carrying out ultrasonic treatment until the solution becomes clear, namely the pretreated porous titanium sheet electrode;
s3: soaking the pretreated porous titanium sheet electrode in the gel for 5-10min until no bubbles are generated;
s4: drying the soaked porous titanium sheet electrode at 80-90 ℃ for 20-30min, then calcining at 700 ℃ for 3-4h, heating at the speed of 5 ℃/min, and generating a catalytic layer on the surface of the porous titanium sheet electrode;
s5: repeating the soaking-drying-calcining process to obtain SrMO3A catalytic electrode.
5. The method for preparing a strontium perovskite catalytic cathode according to claim 3, wherein the method comprises the following steps: the SrMO3The catalytic electrode also comprises the following preparation method: taking a pretreated porous titanium sheet electrode as a cathode and a platinum sheet electrode as an anode, placing the electrodes in an electrodeposition solution at 40-60 ℃, electrodepositing for 20-30min, drying, and then soaking into gel, wherein the electrodeposition solution is a mixed solution of graphene oxide and sodium sulfate.
6. The method for preparing a strontium perovskite catalytic cathode according to claim 5, wherein the method comprises the following steps: the preparation method of the modified graphene oxide comprises the following steps: uniformly mixing graphene oxide and water, carrying out ultrasonic reaction for 1-1.5h, introducing nitrogen, reacting for 0.5-1h, adding a ferrous sulfate solution, reacting for 8-12h, slowly dropwise adding sodium borohydride, continuously reacting for 3-6h, adding nano zinc oxide, reacting for 1-2h, centrifuging, and washing for 4-6 times with water to obtain the modified graphene oxide.
7. The method for preparing a strontium perovskite catalytic cathode according to claim 6, wherein the method comprises the following steps: the preparation method of the nano zinc oxide comprises the following steps: uniformly mixing zinc nitrate and water, adding sodium carboxymethyl cellulose and sodium hydroxide solution, reacting for 1-2h, heating to 120 ℃ for further reaction for 12-15h, washing with ethanol and water for 3-5 times, centrifuging for 5-10min, and drying to obtain the nano zinc oxide.
8. Use of a strontium perovskite catalytic cathode according to any one of claims 1 to 7, wherein: the SrMO3The catalytic electrode is applied to sewage treatment and can catalyze and reduce nitrate in sewage into ammonia nitrogen.
9. Use of a strontium perovskite catalytic cathode according to claim 8, wherein: the SrMO3The catalytic electrode is positioned in the middle of an electrochemical system and serves as a working cathode, and the two reticular ruthenium-iridium electrodes serve as anodes.
10. Use of a strontium perovskite catalytic cathode according to claim 9, wherein: the distance between the cathode and the anode is 1-3cm, and the current density range is 1-6 mA/cm2。
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