CN114477380B - Preparation method of functionalized electrode and application of functionalized electrode in photoelectrocatalysis treatment of solubilized organic sewage - Google Patents
Preparation method of functionalized electrode and application of functionalized electrode in photoelectrocatalysis treatment of solubilized organic sewage Download PDFInfo
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- CN114477380B CN114477380B CN202111634296.9A CN202111634296A CN114477380B CN 114477380 B CN114477380 B CN 114477380B CN 202111634296 A CN202111634296 A CN 202111634296A CN 114477380 B CN114477380 B CN 114477380B
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- 239000010865 sewage Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000005063 solubilization Methods 0.000 claims abstract description 7
- 230000007928 solubilization Effects 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract 2
- 230000000996 additive effect Effects 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 239000004966 Carbon aerogel Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002131 composite material Substances 0.000 claims 2
- 238000000137 annealing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical group OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 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
- C02F1/46109—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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
- C02F2101/301—Detergents, surfactants
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the field of sewage treatment, and discloses a preparation method of a functionalized electrode and application of the functionalized electrode in photoelectrocatalysis treatment and solubilization of organic sewage. The solubilized wastewater has a large amount of surfactant, high concentration of organic pollutants, great environmental hazard and great treatment difficulty. The functionalized electrode in the invention takes conductive glass as a substrate, takes the same kind of surfactant in target solubilization wastewater as an additive to prepare functionalized nano titanium dioxide as a photoelectrocatalyst, and is doped with carbon materials to prepare the photoelectrocatalysis electrode, thereby improving the photoelectrocatalysis efficiency, improving the selectivity of organic pollutants and being beneficial to recycling the residual water after the photoelectrocatalysis treatment.
Description
Technical Field
The invention belongs to the field of organic wastewater treatment, and particularly relates to a preparation method of a functionalized electrode and application of the functionalized electrode in photoelectrocatalysis treatment and solubilization of organic wastewater.
Background
Solubilization of organic wastewater is an unresolved problem in the field of wastewater treatment. The solubilized organic wastewater contains a surfactant and organic contaminants. The concentration of organic contaminants is often greater than its solubility in normal water due to the solubilization of surfactants, which is more harmful to environmental safety and human health than normal organic wastewater. However, the price of the surfactant is high, and the treatment difficulty is high, so that the best strategy for treating the solubilized organic sewage is to degrade the solubilized organic matters as much as possible and keep the surfactant as much as possible for recycling.
In the current literature and patent report, the treatment mode of sewage containing surfactant mostly aims at thoroughly degrading the surfactant, and the foaming effect of the surfactant isolates the communication between sewage and oxygen in the treatment process, so that the treatment effect is difficult to achieve the ideal target. Common treatment modes for solubilized organic sewage include physical adsorption, biological, and advanced oxidation. The adsorbent used in the physical adsorption method is activated carbon or organic bentonite, and the like, although the adsorbent can efficiently adsorb pollutants, the treated adsorbent still needs further effective treatment; the biological method has the advantages that the biological activity of the surfactant is inhibited due to the biotoxicity of the surfactant, and the requirements on degradation environment and operation time are high, so that the biological method is difficult to apply; the advanced oxidation method is one of the most effective methods for treating refractory pollutants at present, but in the scene of treating solubilized organic sewage, the surfactant and the organic pollutants are degraded by high-concentration free radicals together, so that the recovery and the utilization of the surfactant are not facilitated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a functionalized electrode and application of the functionalized electrode in photoelectrocatalysis treatment and solubilization of organic sewage, which have the characteristics of high degradation efficiency, high selectivity of solubilized organic pollutants and reutilization of residual water of a degraded high-concentration surfactant.
A preparation method of a functionalized electrode comprises the following steps:
(1) Selecting conductive glass as a substrate, respectively ultrasonically washing the conductive glass in absolute ethyl alcohol, deionized water and acetone for 20 minutes, and drying for later use;
(2) Mixing the titanium precursor, phthalic acid and the similar surfactant in the solubilised organic sewage, dropwise adding the mixture into an aqueous solution of acetic acid and absolute ethyl alcohol, stirring for 10-300min, and standing for 2-48h to form wet gel; drying at 40-200 deg.c and calcining at 500 deg.c for 0.5-3 hr to obtain functional nanometer titania; in the process of preparing titanium dioxide, the same type of surfactant in sewage is added, and the prepared titanium dioxide and electrode have better catalytic degradation effect in the process of treating solubilizing wastewater, and the principle of the titanium dioxide and electrode is similar to molecular imprinting.
(3) The preparation method comprises the steps of mixing functionalized nano titanium dioxide, a carbon material, terpineol and ethyl cellulose to prepare slurry, wherein the functionalized nano titanium dioxide and the carbon material are used as main bodies for adsorbing and degrading and solubilizing organic pollutants, the ethyl cellulose is used as a cross-linking agent in the electrode preparation process, and the terpineol is used as a slurry solvent. Uniformly mixing the components, uniformly coating the mixture on the conductive glass treated in the step (1), and calcining at 350-500 ℃ for 0.5-3 hours in an oxygen-free environment to prepare the functionalized electrode;
further, in the step (2), the titanium precursor is tetrabutyl titanate or isopropyl titanate or titanium tetrachloride or titanium sulfate or titanyl sulfate;
further, in the step (2), the titanium precursor, phthalic acid and the similar surfactant in the solubilized organic wastewater are in a molar ratio of 1:0.05-0.5:0.01-0.2, preferably in a ratio of 1:0.2-0.4:0.01 to 0.05, further preferred ratio is 1:0.25-0.35:0.01-0.02.
Further, in the step (2), the molar ratio of the aqueous solution of acetic acid and absolute ethyl alcohol to the acetic acid, absolute ethyl alcohol and water is 1:1-10:1-5; the preferred molar ratio is 1:3-7:2-4, further preferred molar ratio is 1:4-5:2-3.
Further, in the step (3), the mass ratio of the titanium dioxide to the carbon material to the terpineol to the ethylcellulose is 1:0.05-2:1-6:0.2-2; the preferred mass ratio is 1:0.05-1.5:2-5:0.3-1, further preferred mass ratio is 1:0.08-0.8:3-5:0.3-0.6.
Further, in the step (3), the carbon material in the slurry is carbon nanotube or graphene or carbon aerogel or carbon xerogel.
Further, in the step (3), the slurry is uniformly coated on a coating prepared from the conductive glass, and the thickness is 1-50 μm. Preferably 5 to 30. Mu.m, more preferably 10 to 20. Mu.m.
In the step (3), the oxygen-free calcination atmosphere means an inert gas atmosphere such as nitrogen or argon.
The functionalized electrode is used as an anode, and the electrode loaded with platinum or carbon element is used as a cathode for photoelectrocatalysis treatment of solubilized organic sewage, and the photoelectrocatalysis treatment is carried out under ultraviolet illumination and external alternating voltage to degrade solubilized organic matters; the organic matters are persistent organic matters such as PAHs, HOCs and the like. The concentration of the solubilized contaminants is 1-100. Mu.g/L.
In the solubilized organic sewage, the inorganic electrolyte is Na 2 SO 4 Or NaCl or K 2 SO 4 Or KCl, with a concentration of 0.02-0.5mol/L. The applied voltage is 0.5-10V, and the alternating frequency is 2-100Hz.
The invention has the advantages and beneficial effects that:
1. the prepared functionalized electrode has higher efficiency on the treatment of solubilized organic sewage, and the degradation rate can reach 91% within 240 min;
2. the prepared functionalized electrode has higher selectivity for treating solubilized organic sewage;
3. the preparation method is simple, the raw materials are cheap, and the preparation method is simple and easy to operate.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
Example 1
In the embodiment, in the treatment of the solubilized organic sewage, the surfactant is sodium dodecyl benzene sulfonate (7.8 mmol/L), and the organic pollutant is naphthalene (30 mmol/L);
(1) Conductive substrate processing
Selecting conductive glass as a substrate, respectively ultrasonically washing the conductive glass in absolute ethyl alcohol, deionized water and acetone for 20 minutes, and drying for later use;
(2) Preparation of functionalized nano titanium dioxide
20g (0.059 mol) of butyl titanate, 3.0g (0.018 mol) of phthalic acid and 0.3g (0.00086 mol) of sodium dodecyl benzene sulfonate are taken and mixed uniformly in a beaker, and 50ml of acetic acid with a molar ratio of 1:4.918:2.648 are slowly added: absolute ethyl alcohol: magnetically stirring the water solution for 30min, and standing at room temperature for 12h to form wet gel; drying at 100 ℃ and calcining at 500 ℃ for 1.5 hours to obtain the functionalized nano titanium dioxide;
(3) Preparation of functionalized electrode
Mixing 1g of functionalized nano titanium dioxide, 0.2g of carbon xerogel, 4g of terpineol and 0.5g of ethyl cellulose in a mortar for 2h, preparing slurry by mixing, and coating in a screen printing modeIs distributed on the surface of the treated conductive glass, and the electrode area is 9cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying the electrode, performing high-temperature treatment in a tube furnace under nitrogen gas, heating at a speed of 2 ℃/min, and preserving heat for 0.5 hour after heating to 350 ℃; naturally cooling to room temperature to obtain the sodium dodecyl benzene sulfonate functionalized electrode;
photoelectrocatalytic treatment of solubilized organic wastewater
In the solubilized organic sewage, the surfactant is sodium dodecyl benzene sulfonate (7.8 mmol/L), and the organic pollutant is naphthalene (30 mmol/L); adding 50ml of the solubilized organic sewage into an electrolytic cell, and adding 0.58g of NaCl; the sodium dodecyl benzene sulfonate functionalized electrode is taken as an anode, and the platinum electrode is taken as a cathode; the photoelectrocatalytic degradation parameters were as follows: under the irradiation of an ultraviolet lamp, the applied voltage is 4V, the alternating frequency of the voltages of the two electrodes is 20Hz, the degradation time is 160min, the concentration of naphthalene is measured by liquid chromatography, and the degradation efficiency is 85.6%.
Example 2
In the embodiment, in the treatment of the solubilized organic sewage, the surfactant is sodium dodecyl sulfate (20 mmol/L), and the organic pollutant is phenanthrene (40 mmol/L);
(1) Conductive substrate processing
Selecting conductive glass as a substrate, respectively ultrasonically washing the conductive glass in absolute ethyl alcohol, deionized water and acetone for 20 minutes, and drying for later use;
(2) Preparation of functionalized nano titanium dioxide
18g (0.063 mol) of isopropyl titanate, 3.6g (0.02 mol) of phthalic acid, 0.33g (0.0011 mol) of sodium dodecyl sulfate were taken and mixed well in a beaker, 50ml of a molar ratio 1 were slowly added: 3:2.2 acetic acid: absolute ethyl alcohol: magnetically stirring the water solution for 30min, and standing at room temperature for 12h to form wet gel; drying at 80 ℃ and calcining at 450 ℃ for 2.5 hours to obtain the functionalized nano titanium dioxide;
(3) Preparation of functionalized electrode
Mixing 1g of functionalized nano titanium dioxide, 0.08g of carbon nano tube, 3.5g of terpineol and 0.6g of ethyl cellulose in a mortar for 30min, preparing slurry by mixing, and coating in a screen printing modeOn the surface of the treated conductive glass, the electrode area was 9cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying the electrode, performing high-temperature treatment in a tube furnace under argon gas treatment atmosphere, heating at a speed of 3 ℃/min, and preserving heat for 1.5 hours after heating to 450 ℃; naturally cooling to room temperature to obtain the sodium dodecyl benzene sulfonate functionalized electrode;
photoelectrocatalytic treatment of solubilized organic wastewater
In the solubilized organic sewage, the surfactant is sodium dodecyl sulfate (20 mmol/L), and the organic pollutant is phenanthrene (40 mmol/L); adding 50ml of the solubilized organic sewage into an electrolytic cell, and adding 0.77g of Na 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The functional electrode of sodium dodecyl sulfate is taken as an anode, and the platinum electrode is taken as a cathode; the photoelectrocatalytic degradation parameters were as follows: under the irradiation of an ultraviolet lamp, the external voltage is 3.5V, the alternating frequency of the voltages of the two electrodes is 40Hz, the degradation time is 180min, the concentration of naphthalene is measured by liquid chromatography, and the degradation efficiency of phenanthrene is measured to be 90.5%.
Example 3
In the embodiment, in the treatment of the solubilized organic sewage, the surfactant is TX-100 (50 mmol/L), and the organic pollution organic matter is pentachlorophenol (20 mmol/L);
(1) Conductive substrate processing
Selecting conductive glass as a substrate, respectively ultrasonically washing the conductive glass in absolute ethyl alcohol, deionized water and acetone for 20 minutes, and drying for later use;
(2) Preparation of functionalized nano titanium dioxide
25g (0.15 mol) of titanyl sulfate, 5.05g (0.03 mol) of phthalic acid, 1.6g (0.0025 mol) of TX-100 are taken and mixed homogeneously in a beaker, 50ml of a molar ratio 1 are added slowly: 7: acetic acid of 2.5: absolute ethyl alcohol: magnetically stirring the water solution for 30min, and standing at room temperature for 12h to form wet gel; drying at 150 ℃ and calcining at 400 ℃ for 2.5 hours to obtain the functionalized nano titanium dioxide;
(3) Preparation of functionalized electrode
Mixing 1g of functionalized nano titanium dioxide, 1g of carbon aerogel, 5.5 terpineol and 1.5g of ethyl cellulose in a mortar for 2 hours, preparing slurry by mixing, and coating the slurry on a treatment device in a screen printing modeSurface of the conductive glass, electrode area was 9cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Drying the electrode, performing high-temperature treatment in a tube furnace under nitrogen gas, heating at a speed of 2.5 ℃/min, and preserving heat for 1 hour after heating to 450 ℃; naturally cooling to room temperature to obtain the sodium dodecyl benzene sulfonate functionalized electrode;
photoelectrocatalytic treatment of solubilized organic wastewater
In the solubilized organic sewage, the surfactant is TX-100 (500 mmol/L), the organic pollutant is pentachlorophenol (20 mmol/L), 50ml of the solubilized organic sewage is added into an electrolytic cell, and 0.86g KCl is added; taking a TX-100 functionalized electrode as an anode and a platinum electrode as a cathode; the photoelectrocatalytic degradation parameters were as follows: under the irradiation of an ultraviolet lamp, the external voltage is 10V, the alternating frequency of the voltages of the two electrodes is 50Hz, the degradation time is 180min, the concentration of naphthalene is measured by liquid chromatography, and the photoelectrocatalysis degradation efficiency of pentachlorophenol is 80.7%.
Comparative example 1
The difference from example 1 is that sodium dodecyl benzene sulfonate is not added to the functionalized nano-titanium dioxide prepared in the step (2), and the sodium dodecyl benzene sulfonate is used in the same evaluation system as example 1, so that the naphthalene degradation efficiency is only 67.26%.
Comparative example 2
The difference from example 1 is that the surfactant added in the preparation of the functionalized nano titanium dioxide in the step (2) is 5.0g of TX-100, which is used in the same evaluation system as in example 1, and the naphthalene degradation efficiency is 72.91%.
Table 1 summary of parameters in each experimental and comparative group
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of a functionalized electrode is characterized by comprising the following steps: the method comprises the steps of taking conductive glass as a substrate, taking the same kind of surfactant in target solubilization wastewater as an additive to prepare functionalized nano titanium dioxide as a photoelectric catalyst, doping carbon materials to prepare composite slurry, coating the composite slurry on the conductive glass, and annealing in an anaerobic environment to prepare an electrode, wherein the method comprises the following steps of:
the method comprises the steps of (1) mixing a titanium precursor, phthalic acid and a similar surfactant in solubilized organic sewage in a molar ratio of 1:0.05-0.5: mixing 0.01-0.2, and dropwise adding the mixture into a mixture in a molar ratio of 1:1-10:1-2.5 acetic acid: absolute ethyl alcohol: stirring the solution in water for 10-300min, and standing for 2-48h to form wet gel; drying at 40-200 deg.c and calcining at 500 deg.c for 0.5-3 hr to obtain functional nanometer titania; functionalized nano titanium dioxide, carbon material, terpineol and ethyl cellulose are mixed according to the following ratio of 1:0.05-2:1-6: mixing the materials according to the mass ratio of 0.2-2 to prepare slurry, uniformly coating the slurry on conductive glass, and calcining the conductive glass at 350-500 ℃ for 0.5-3 hours in an oxygen-free environment to obtain the functionalized electrode.
2. The method of manufacturing according to claim 1, characterized in that: the titanium precursor is tetrabutyl titanate or isopropyl titanate or titanium tetrachloride or titanium sulfate or titanyl sulfate.
3. The method of manufacturing according to claim 1, characterized in that: the carbon material is carbon nano tube or graphene or carbon aerogel or carbon xerogel.
4. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the similar surfactants in the titanium precursor, the phthalic acid and the solubilized organic sewage is 1:0.25-0.35:0.01-0.02.
5. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the functionalized nano titanium dioxide to the carbon material to the terpineol to the ethyl cellulose is 1:0.08-0.8:3-5:0.3-0.6.
6. The use of the functionalized electrode prepared by the preparation method according to claim 1 in the photoelectrocatalysis treatment of solubilized organic wastewater.
7. The use according to claim 6, characterized in that: the functionalized electrode is used as an anode, and the electrode of platinum or carbon element is used as a cathode.
8. The use according to claim 6, characterized in that: the pollutants in the solubilized organic sewage are PAHs and HOCs, and the concentration of the pollutants is 1-100 mug/L.
9. The use according to claim 6, characterized in that: the inorganic electrolyte adopted by the photoelectrocatalysis treatment is Na 2 SO 4 Or NaCl or K 2 SO 4 Or KCl, with a concentration of 0.02-0.5mol/L.
10. The use according to claim 6, characterized in that: the photoelectrocatalysis treatment is that under the irradiation of an ultraviolet lamp and the external voltage, the two electrodes perform voltage conversion at the alternating frequency of 2-100Hz.
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