CN117003340A - Device for degrading organic pollutants by utilizing primary cell-like effect and application thereof - Google Patents
Device for degrading organic pollutants by utilizing primary cell-like effect and application thereof Download PDFInfo
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- CN117003340A CN117003340A CN202310733397.4A CN202310733397A CN117003340A CN 117003340 A CN117003340 A CN 117003340A CN 202310733397 A CN202310733397 A CN 202310733397A CN 117003340 A CN117003340 A CN 117003340A
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- 230000000694 effects Effects 0.000 title claims abstract description 22
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 21
- 230000000593 degrading effect Effects 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000000356 contaminant Substances 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 6
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 31
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 125000005385 peroxodisulfate group Chemical group 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 241000252212 Danio rerio Species 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 peroxodisulfate ions Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 description 2
- 238000011047 acute toxicity test Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46176—Galvanic cells
-
- 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
-
- 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
-
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
-
- 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
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/008—Mobile apparatus and plants, e.g. mounted on a vehicle
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
Abstract
The invention discloses a device for degrading organic pollutants by utilizing a galvanic cell-like effect and an application of degrading bisphenol A in wastewater, comprising the following steps: a reactor with openings at two ends; a proton exchange membrane sealed at one end of the reactor and having an opening; a cathode electrode supporting a copper single-atom carbon-based catalyst disposed in the reactor; the buoyancy device is arranged on the reactor, and exposes an opening at the other end of the reactor to the liquid level for treatment; an aqueous potassium peroxodisulfate solution disposed in the reactor; the invention relates to an anode electrode of a copper-loaded single-atom carbon-based catalyst connected with a potassium persulfate aqueous solution through a lead. The device designed and prepared by the invention can transfer electrons through the wire to degrade bisphenol A in the water body by the galvanic cell-like effect, can degrade organic pollutants while avoiding adding oxidant (peroxodisulfate) directly into the water body, and reduces the harm of the peroxodisulfate to the water body biology, so that the device can be better applied to the field of water pollution control.
Description
Technical Field
The invention belongs to the technical fields of material engineering and environmental engineering, and relates to a device for degrading organic pollutants by utilizing a primary cell-like effect and application of the device in wastewater treatment.
Background
Active oxygen species generated by catalytic activation of the oxides (such as persulfates and hydrogen peroxide) have high redox capability, play a leading role in vitro and in vivo biological/chemical treatment, degradation of organic pollutants difficult to degrade and the like, and can quickly kill/destroy cancer cells and organic molecular structures. In terms of water treatment, advanced Oxidation (AOP) is a very promising technology for the treatment of refractory organic pollutants. However, in a body of water where aquatic organisms are present, the presence of oxidants and reactive oxygen species produced thereby may cause damage to healthy cells or organisms and the disposal of residual oxidants often requires additional consumption. Meanwhile, in order to recycle and eliminate additional pollution, the catalyst needs to be recovered from the water body, and the powder catalyst which is currently widely studied faces the big problem of difficult recovery. Thus, degradation of organic contaminants based on persulfate activation is hindered in practical applications of the process.
The device designed and prepared in the invention can transfer electrons through the wire to degrade bisphenol A in the water body by the galvanic cell-like effect, can degrade organic pollutants while avoiding adding oxidant (peroxodisulfate) directly into the water body, and reduces the harm of the peroxodisulfate to the water body organisms, so that the device can be better applied to the field of water pollution control.
Disclosure of Invention
The invention provides a device for degrading organic pollutants by utilizing a galvanic cell-like effect and application thereof, a preparation method of the device for degrading organic pollutants by utilizing the galvanic cell-like effect and application of the device in wastewater treatment, a proton exchange membrane is utilized to prevent persulfate from leaking into a water body to be treated, and electrodes prepared by a copper monoatomic catalyst activate the persulfate and a lead transfer electron to degrade the pollutants.
An apparatus for degrading organic contaminants using a galvanic-like effect, comprising:
a reactor with openings at two ends;
a proton exchange membrane sealed at one end of the reactor and having an opening;
a cathode electrode supporting a copper single-atom carbon-based catalyst disposed in the reactor;
the buoyancy device is arranged on the reactor, and exposes an opening at the other end of the reactor to the treatment liquid level;
an aqueous potassium peroxodisulfate solution disposed within the reactor;
and an anode electrode of a copper-loaded single-atom carbon-based catalyst connected with the potassium persulfate aqueous solution through a lead.
The anode electrode of the copper-loaded single-atom carbon-based catalyst is arranged on the buoyancy device.
The proton exchange membrane is a cation exchange membrane.
The proton exchange membrane is a Nafion membrane.
The cathode electrode of the supported copper single-atom carbon-based catalyst comprises: carbon felt and Cu-N-C catalyst coated on the carbon felt.
The anode electrode of the supported copper single-atom carbon-based catalyst comprises: carbon felt and Cu-N-C catalyst coated on the carbon felt.
The device for degrading organic pollutants by utilizing the galvanic cell-like effect is applied to degrading the organic pollutants. The application is that the organic pollutant is bisphenol A, phenol, 2, 4-dichlorophenol and 4-chlorophenol.
When the reactor contains potassium persulfate solution and is placed on water to be treated containing organic pollutants, the degradation reaction is activated, and the whole reaction process and principle are as follows: 1) Organic matters in the wastewater are contacted with an anode electrode of a reactor, and peroxodisulfate ions in the device are contacted with a cathode electrode; 2) The potential of the positive electrode is reduced due to contact with organic matters, and the potential of the negative electrode is increased due to contact with peroxodisulfate ions; 3) When the potential of the negative electrode rises to be higher than the oxidation-reduction potential of the organic pollutant in contact with the positive electrode, the organic pollutant loses electrons and is transferred to the peroxodisulfate ions in contact with the negative electrode through the positive electrode, the lead and the negative electrode in sequence; 4) Finally, the organic pollutant loses electrons and is oxidized and degraded, the electrons are reduced into sulfate ions by the peroxodisulfate ions, and protons are transferred through a proton exchange membrane to maintain the electric neutrality of the solution.
Most preferablyThe treatment conditions of the invention are as follows: a device for degrading organic pollutants by using a galvanic cell-like effect seals one end of a hollow cylindrical quartz tube by a proton exchange membrane (Nafion membrane), and enables the quartz tube to stably float on the water surface by using ethylene-vinyl acetate copolymer foam (EVA foam). Simultaneously, mixing 200mg of prepared copper single-atom powder catalyst, 20mL of deionized water, 20mL of absolute ethyl alcohol and 200 mu L of perfluorosulfonic acid resin solution, carrying out ultrasonic treatment for 1 hour to obtain a uniform solution, then dripping the uniform solution onto a cut and cleaned graphite felt, and drying at 40 ℃ to obtain the catalyst with the concentration of 1mg/cm -2 Is provided. 40mL of 10mM potassium peroxodisulfate solution is placed in a sealed quartz tube, a bisphenol A solution (volume of 2L, concentration of 5 μm) containing 500ppm sodium chloride (salinity of 0.5% per mill) is prepared in the water to be treated, and then two catalytic electrodes (specification of 3cm×3cm×0.2cm and 6cm×4cm×0.2cm, respectively) are placed in the quartz tube and the water to be treated, and connected by using platinum wires as wires, namely catalytic reaction is carried out.
The invention has the following outstanding characteristics and beneficial effects:
(1) The device prepared by the method can enable the catalytic electrode to activate the peroxydisulfate to degrade organic pollutants through the similar primary cell effect, and avoid secondary pollution caused by directly putting the peroxydisulfate into water.
(2) The device can stably float on the water surface, and is convenient for recycling after the degradation reaction is finished.
Drawings
FIG. 1 is a schematic view of catalytic electrode synthesis and characterization of the electrode, wherein (a) is a schematic view of Graphite Felt (GF) electrode Cu-N-C@GF synthesis containing a copper monoatomic catalyst (Cu-N-C), (b) is a Scanning Electron Microscope (SEM) view of unsupported Graphite Felt (GF), (C) is a Scanning Electron Microscope (SEM) view of Cu-N-C@GF, and (d) is a Cu-N-C@GF element distribution diagram.
FIG. 2 is a photograph of a device of a galvanic cell-like reaction.
FIG. 3 shows the degradation curve of the device for this type of galvanic reaction for the catalytic degradation of bisphenol A.
FIG. 4 shows an electrochemical correlation test of Cu-N-C@GF, wherein (a) is a schematic diagram of open circuit potential curves and potential differences on different system electrodes, and (b) is a timing current curve on different system electrodes.
FIG. 5 is a cyclic voltammogram over different system electrodes.
Fig. 6 shows acute toxicity test of zebra fish, wherein (a) is a photograph of zebra fish under different conditions, and (b) is mortality of zebra fish under different conditions.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
The preparation method of the copper single-atom powder catalyst comprises the following steps: first, 2.092g of copper acetate monohydrate and 0.771g of L-glutamic acid were dissolved in 500mL of deionized water to obtain a solution A; 1.16g of 1,3, 5-trimesic acid was dissolved in a mixture of 450mL of deionized water and 50mL of ethanol to give solution B. Then, after mixing the solution A and the solution B and stirring for two hours at room temperature of 25 ℃, the precipitate obtained by centrifugal separation is dried for 12 hours at 60 ℃ to prepare blue solid powder Cu (BTC) (H 2 O) 3 MOF. Then 0.2g of Cu (BTC) (H 2 O) 3 The MOF and 2g dicyandiamide were homogenized, the mixture was placed in a tube furnace and calcined in an argon atmosphere at 800 degrees Celsius for 5 hours at a ramp rate of 5 degrees Celsius per minute. Finally, the obtained powder is soaked in 40mL of oxygen saturated hydrochloric acid aqueous solution with the mass fraction of 5% for 4 hours, and then deionized water is used for washing the powder to be neutral, so that the copper monoatomic powder catalyst is prepared.
(1) The method of the invention is used for the treatment process
One end of a hollow cylindrical quartz tube was sealed with a proton exchange membrane (Nafion membrane) and allowed to float stably on the water surface using an ethylene-vinyl acetate copolymer foam (EVA foam). Simultaneously, mixing 200mg of prepared copper single-atom powder catalyst, 20mL of deionized water, 20mL of absolute ethyl alcohol and 200 mu L of perfluorosulfonic acid resin solution, carrying out ultrasonic treatment for 1 hour to obtain a uniform solution, then dripping the uniform solution onto a cut and cleaned graphite felt, and drying at 40 ℃ to obtain the catalyst with the concentration of 1mg/cm -2 Is provided. 40mL of 10mM potassium peroxodisulfate solution were placed in a sealed quartz tube, ready to be placedThe method comprises preparing bisphenol A solution (volume of 2L, concentration of 5 μm) containing 500ppm sodium chloride (salinity of 0.5%o) in water, placing two catalytic electrodes (specification of 3cm×3cm×0.2cm and 6cm×4cm×0.2 cm) respectively in quartz tube and water to be treated, and connecting with platinum wire as wire to perform catalytic degradation reaction.
The bisphenol A concentration detection method comprises the following steps: taking 1mL of reaction solution at preset time intervals, and detecting residual bisphenol A on high performance liquid chromatography, wherein the liquid phase condition is methanol: water=70:30.
(2) Effects obtained by this embodiment
Electron microscopy and elemental scanning of the catalytic electrode are shown in fig. 1. The preparation of the catalyst electrode is schematically shown in (a), which shows that the catalyst electrode is formed by coating a graphite felt with a powdery catalyst, and (b) and (c) the original graphite felt without the catalyst and the graphite felt with the catalyst can be used for seeing that graphite felt fibers are smooth from the original surface, and irregular particles appear on the surface of the fibers after the loading, which shows that the catalyst is successfully loaded. (d) The element distribution diagram shows that Cu-N-C@GF contains copper and nitrogen and is uniformly distributed, and further shows that the catalyst loading is successful.
As shown in FIG. 2, the prepared graphite felt electrodes (the specifications are respectively 3cm multiplied by 0.2cm and 6cm multiplied by 4cm multiplied by 0.2 cm), a wire, a cylindrical tube with one end sealed by a Nafion film, EVA foam and the like are assembled together to form the device similar to a primary cell reaction, and the device can stably float on the water surface and avoid the PDS solution from leaking into the water body to be treated. Wherein, the figures a and b are schematic diagrams and photographs of the device when the device is on the water surface to be treated respectively, the figure c is a structural diagram of the device, 1 is a reactor with two open ends, 2 is a lead wire for connecting a cathode electrode and an anode electrode, 3 is EVA foam for providing buoyancy, 4 is PDS solution which is arranged in the reactor, 5 is a cathode electrode, 6 is a Nafion membrane for sealing one end of the reactor, and 7 is an anode electrode.
As shown in FIG. 3, when two catalytic electrodes are not connected by a wire, the adsorption effect of the electrode on bisphenol A is reflected, and 10% of bisphenol A in water can be adsorbed; when two catalytic electrodes are connected by a wire, but there is no PDS solution in the cylindrical tube, bisphenol a will also be slightly reduced due to the adsorption capacity of the electrodes themselves; when the degradation reaction was started (electrodes connected by wires and cylindrical tube containing 10mM PDS solution), 2L of bisphenol A5. Mu.M could be removed within 3 hours, indicating a better effect of the catalytic electrode.
As shown in fig. 4, the electrochemical correlation experiment shows that the degradation reaction can be completed by electron transfer. (a) In order to catalyze the open-circuit voltage under different systems of the electrode, the potential of Cu-N-C@GF is approximately 0.37V, and after bisphenol A is added into the system, the potential is reduced and stabilized at 0.27V; in contrast, after PDS was added to the system, the potential was raised and stabilized at 0.77V. Applying a constant potential to Cu-N-C@GF by the potential measured in (a) to obtain a timing current curve shown in (b), wherein when the applied potential is constant at 0.37V (equivalent to the potential of Cu-N-C@GF itself), no matter whether BPA exists in the system or not, the current response does not change obviously; when the applied potential is constant at 0.77V (equivalent to the stable potential after the Cu-N-C@GF is contacted with PDS), the current is obviously improved in a system containing BPA compared with a system without BPA, which indicates that the high potential after the Cu-N-C@GF is contacted with PDS is enough for the BPA to exchange electrons with the surface of a catalytic electrode.
As shown in fig. 5, the cyclic voltammetry characteristic of the catalytic electrode of fig. 5 with/without BPA in the system further illustrates that BPA can undergo oxidation reactions at the catalytic electrode surface, which together with fig. 4 shows that the device causes degradation of BPA to be a galvanic-like reaction.
As shown in fig. 6, (a) is a photograph of the acute toxicity test of zebra fish, and (b) is a test result. When the water environment in which the zebra fish survives contains 1mM PDS (concentration in powder catalysis), the death rate of the zebra fish is up to more than 90% in 2 hours, and the zebra fish is dead in 5 hours, but the water environment using the primary cell reaction device does not cause obvious death of the zebra fish in 5 hours, which indicates that the device can avoid secondary pollution caused by directly putting the PDS into water.
Claims (8)
1. An apparatus for degrading organic contaminants using a galvanic-like effect, comprising:
a reactor with openings at two ends;
a proton exchange membrane sealed at one end of the reactor and having an opening;
a cathode electrode supporting a copper single-atom carbon-based catalyst disposed in the reactor;
the buoyancy device is arranged on the reactor, and exposes an opening at the other end of the reactor to the treatment liquid level;
an aqueous potassium peroxodisulfate solution disposed within the reactor;
and an anode electrode of a copper-loaded single-atom carbon-based catalyst connected with the potassium persulfate aqueous solution through a lead.
2. The apparatus for degrading organic contaminants utilizing a galvanic-like effect according to claim 1 wherein said anode electrode supporting a copper monatomic carbon-based catalyst is disposed on said buoyancy device.
3. The apparatus for degrading organic contaminants utilizing a galvanic cell-like effect according to claim 1 wherein said proton exchange membrane is a cation exchange membrane.
4. The apparatus for degrading organic contaminants utilizing a galvanic-like effect according to claim 1 wherein said proton exchange membrane is a Nafion membrane.
5. The apparatus for degrading organic contaminants utilizing a galvanic-like effect according to claim 1 wherein said copper-supported single-atom carbon-based catalyst cathode electrode includes: carbon felt and Cu-N-C catalyst coated on the carbon felt.
6. The apparatus for degrading organic contaminants utilizing a galvanic-like effect according to claim 1 wherein said anode electrode supporting a copper monatomic carbon-based catalyst comprises: carbon felt and Cu-N-C catalyst coated on the carbon felt.
7. Use of a device for degrading organic pollutants using a galvanic-like effect according to any of claims 1 to 6 for degrading organic pollutants.
8. The use according to claim 7, wherein the organic contaminant is one or more of bisphenol a, phenol, 2, 4-dichlorophenol, 4-chlorophenol.
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|---|---|---|---|
| CN202310733397.4A CN117003340A (en) | 2023-06-20 | 2023-06-20 | Device for degrading organic pollutants by utilizing primary cell-like effect and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310733397.4A CN117003340A (en) | 2023-06-20 | 2023-06-20 | Device for degrading organic pollutants by utilizing primary cell-like effect and application thereof |
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| CN202310733397.4A Pending CN117003340A (en) | 2023-06-20 | 2023-06-20 | Device for degrading organic pollutants by utilizing primary cell-like effect and application thereof |
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