CN110783111A - Titanium dioxide film electrode and preparation method and application thereof - Google Patents
Titanium dioxide film electrode and preparation method and application thereof Download PDFInfo
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- CN110783111A CN110783111A CN201911010347.3A CN201911010347A CN110783111A CN 110783111 A CN110783111 A CN 110783111A CN 201911010347 A CN201911010347 A CN 201911010347A CN 110783111 A CN110783111 A CN 110783111A
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- titanium dioxide
- film electrode
- thin film
- dioxide thin
- sodium sulfate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 70
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 54
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 54
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 52
- 239000010409 thin film Substances 0.000 claims abstract description 47
- 230000000593 degrading effect Effects 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 35
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 33
- 239000010408 film Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 12
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 19
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 18
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 6
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 6
- 229960003405 ciprofloxacin Drugs 0.000 claims description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 42
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000000969 carrier Substances 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000004298 light response Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000010248 power generation Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/1216—Metal oxides
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Abstract
The invention provides a titanium dioxide film electrode and a preparation method and application thereof, wherein FTO conductive glass is immersed in a mixed solution obtained by mixing antimony trichloride, tetrabutyl titanate and a hydrochloric acid solution, and reacts for 4-8 h at the temperature of 150-180 ℃; and (3) carrying out heat treatment for 2-6 h at 400-500 ℃ after cooling, washing and drying to obtain the titanium dioxide film electrode. Combining the titanium dioxide thin film electrode and the monocrystalline silicon cell slice to obtain a photo-anode; the anode of the photocell is a photoanode, the cathode of the photocell is a platinum electrode, the electrolyte of the photocell is a sodium sulfate aqueous solution, and the photocell can be used for degrading organic matters in water. The titanium dioxide thin film electrode has good visible light response and photocatalysis performance, can effectively inhibit the recombination of photon-generated carriers and promote the separation of photon-generated electrons and holes; the photoanode can be used for degrading organic matters in water under the irradiation of sunlight, and can simultaneously generate hydrogen without additional voltage supply.
Description
Technical Field
The invention relates to the field of materials for wastewater treatment, and particularly relates to a titanium dioxide film electrode and a preparation method and application thereof.
Background
The treatment of wastewater using solar energy is considered to be a very potential and promising technology. The hydrogen producing technology by photoelectrocatalysis water decomposition is that semiconductor photocatalyst generates photon-generated carriers (electron-hole) and H in water under the irradiation of sunlight with a certain wavelength
+And OH
-A process of generating hydrogen and oxygen by an oxidation-reduction reaction occurs. Photocatalysis is applied to the sewage treatment industry, and hydroxyl radicals with strong oxidizing property generated in the photocatalysis process can oxidize refractory organic matters. However, photo-generated electrons and holes are easily combined in the photocatalysis process, so that the light quantum efficiency of photocatalytic water splitting hydrogen production and photocatalytic organic pollutant degradation is very low. In order to further improve the photocatalytic efficiency, most researchers improve the degradation efficiency by applying a voltage, but applying a voltage increases the energy consumption.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a titanium dioxide film electrode and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a titanium dioxide thin film electrode, comprising the steps of:
(1) dissolving antimony trichloride and tetrabutyl titanate in a hydrochloric acid solution to obtain a mixed solution A;
(2) immersing FTO conductive glass in the mixed solution A in a closed reaction container, and then reacting for 4-8 h at 150-180 ℃;
(3) and (3) washing the FTO conductive glass treated in the step (2) with deionized water after cooling, drying, and then carrying out heat treatment at 400-500 ℃ for 2-6 h to obtain the titanium dioxide film electrode.
The titanium dioxide thin film electrode prepared by the method is TiO doped with antimony (Sb)
2The Sb on the nanotube array film electrode and the titanium dioxide film electrode is uniformly and orderly dispersed in the TiO
2The titanium dioxide thin film electrode prepared by the method has good visible light response and photocatalysis performance, and the titanium dioxide thin film electrode prepared by the method has good mechanical stability and long service life; the titanium dioxide film electrode prepared by the method can generate strong oxidative hydroxyl free radicals and other active oxygen under the irradiation of light to oxidize and mineralize organic pollutants, and can be used for organic wastewater treatment; the titanium dioxide thin film electrode prepared by the method can effectively inhibit the recombination of photon-generated carriers, promote the separation of photon-generated electrons and holes, and realize the effective utilization of the photon-generated carriers.
Preferably, the molar ratio of the antimony trichloride to the tetrabutyl titanate in the mixed solution A is 1: 8-9.
The inventor finds that in the preparation method of the titanium dioxide thin film electrode, when the molar ratio of antimony trichloride to tetrabutyl titanate in the mixed solution A is 1: 8-9, the prepared titanium dioxide thin film electrode has better visible light response and photocatalytic performance.
Preferably, in the step (1), the mass concentration of the hydrochloric acid solution is 15% -20%, and the concentration of antimony trichloride in the mixed solution A is 4-5 mmol/L.
The inventor finds that in the preparation method of the titanium dioxide thin film electrode, when the mass concentration of the hydrochloric acid solution in the step (1) is 15% -20%, and the concentration of antimony trichloride in the mixed solution A is 4-5 mmol/L, Sb on the prepared titanium dioxide thin film electrode can be uniformly and orderly dispersed in TiO
2The tube wall of the nanotube and the titanium dioxide thin film electrode have better performance of inhibiting the recombination of photon-generated carriers and promoting the separation of photon-generated electrons and holes.
Preferably, in the step (2), the reaction is carried out for 6h at 170 ℃, and in the step (3), the heat treatment is carried out for 4h at 500 ℃.
Preferably, in the step (2), the closed reaction vessel is a high-pressure reaction kettle with a polytetrafluoroethylene lining.
Preferably, in the step (3), the drying manner is as follows: drying for 3-7 h at 80 ℃.
The invention also provides a titanium dioxide thin film electrode prepared by any one of the methods.
The invention also provides a photo-anode, which comprises a monocrystalline silicon cell piece and the titanium dioxide film electrode, wherein the anode on the back surface of the monocrystalline silicon cell piece is connected with the front surface of the titanium dioxide film electrode through a lead A, the lead A is connected in a welding or conductive silver adhesive bonding mode, the cathode on the back surface of the monocrystalline silicon cell piece is connected with a lead B, the front surface of the monocrystalline silicon cell piece and the back surface of the titanium dioxide film electrode are overlapped together, and the side surface of the titanium dioxide film electrode, the back surface of the monocrystalline silicon cell piece and the side surface of the monocrystalline silicon cell piece are coated with insulating epoxy resin coatings.
The photo-anode can form good complementation between a monocrystalline silicon cell and the titanium dioxide thin film electrode, the titanium dioxide thin film electrode absorbs short-wave light in the atmosphere, and long-wave light is effectively absorbed by a monocrystalline silicon photovoltaic cell after penetrating through the titanium dioxide thin film electrode, so that sunlight can be fully utilized; the photo-anode can be used for degrading organic matters in water under the irradiation of sunlight and can generate hydrogen simultaneously, so that the degradation of the organic matters in wastewater and the high-efficiency combination of hydrogen preparation can be realized simultaneously, voltage does not need to be additionally provided, other energy sources do not need to be consumed, light only needs to be utilized, energy can be saved, and the efficiency of generating the hydrogen is high.
The invention also provides a photocell, wherein the anode of the photocell is the photo-anode, the cathode of the photocell is a platinum electrode, and the electrolyte of the photocell is 0.1-0.5M sodium sulfate aqueous solution.
The photocell can be used for degrading organic matters in wastewater, does not need to consume other energy sources, and only needs to utilize light.
The invention also provides a method for degrading organic matters, which comprises the following steps:
soaking a platinum electrode and the photo-anode in a sodium sulfate aqueous solution of 0.1-0.5M in parallel at a certain distance, and connecting the platinum electrode and the photo-anode outside the sodium sulfate aqueous solution by a lead;
(II) putting organic pollutants into the sodium sulfate aqueous solution in the step (I);
(III) irradiating the photo-anode with light.
The method forms an electrolysis system by utilizing the platinum electrode, the photo-anode and the electrolyte, can degrade organic matters in the electrolyte only under illumination, also generates clean energy hydrogen, does not need to provide additional bias voltage, reduces the power consumption of electrolyzed water, can well utilize the coupling of photoelectrocatalysis, improves the hydrogen production efficiency, can realize resource utilization of various waste water, does not generate secondary pollution, and can keep good effect under long-time operation.
Preferably, the wavelength of the light in the step (3) is 420nm to 1200nm, and the intensity of the light is 100mW cm
-2The organic matter includes at least one of 2-chlorophenol (2-CP), Methyl Orange (MO), Methylene Blue (MB), rhodamine B (RHB), Atrazine (ATZ), Ciprofloxacin (CIP), bisphenol A (BPA), and dichlorophenoxyacetic acid (2, 4-D).
The inventor finds that the degradation efficiency of the organic matters is better under the illumination condition.
The invention has the beneficial effects that: the titanium dioxide thin film electrode prepared by the method has good visible light response and photocatalysis performance, good mechanical stability and long service life, can be used for organic wastewater treatment, can effectively inhibit the recombination of photon-generated carriers, promotes the separation of photon-generated electrons and holes, and realizes the effective utilization of the photon-generated carriers; the photo-anode can be used for degrading organic matters in water under the irradiation of sunlight, can simultaneously generate hydrogen, can simultaneously realize the efficient combination of the degradation of the organic matters in the wastewater and the preparation of the hydrogen, and does not need to additionally provide voltage; the method for degrading the organic matters forms an electrolysis system by utilizing the platinum electrode, the photo-anode and the electrolyte, can degrade the organic matters in the electrolyte only by illumination, generates clean energy hydrogen, does not need to provide additional bias voltage, reduces the power consumption of electrolyzed water, can well utilize the coupling of photoelectrocatalysis, improves the hydrogen production efficiency, can realize resource utilization of various waste water, does not generate secondary pollution, and can keep good effect under long-time operation.
Drawings
Fig. 1 is a schematic view illustrating a method for degrading organic substances according to an embodiment of the present invention. Wherein, 1 represents a titanium dioxide thin film electrode, 2 represents a monocrystalline silicon battery piece, and 3 represents a platinum electrode.
FIG. 2 is a schematic assembly diagram of a photoanode according to an embodiment of the invention; wherein, (a) is a titanium dioxide thin film electrode, (b) is a monocrystalline silicon battery piece, (c) is a side schematic view of the photo-anode, and (d) is a front schematic view of the photo-anode.
Fig. 3 is a graph showing a light absorption curve and a light transmittance curve of the photo-anode according to the embodiment of the present invention. Line 1 represents the absorbance of the monocrystalline silicon cell piece in the photo-anode, and line 2 represents the light transmittance curve of the titanium dioxide thin film electrode in the photo-anode.
FIG. 4 is a diagram illustrating an effect of the method for degrading organic substances according to the embodiment of the present invention. Wherein 1 is the removal rate of 2-CP; 2 is the TOC removal rate.
Fig. 5 is a graph showing battery performance of an electrolysis system according to an embodiment of the present invention.
FIG. 6 is a graph showing current density and hydrogen production rate of the method for degrading an organic substance according to the embodiment of the present invention. Wherein 1 is a change curve of current density along with time; 2 is a change curve of hydrogen production with time.
Fig. 7 is a graph illustrating a long-term stability test of current density in a sodium sulfate solution according to a method for degrading an organic substance according to an embodiment of the present invention.
FIG. 8 is a diagram illustrating the repetitive effects of the method for degrading organic substances according to the embodiment of the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the titanium dioxide thin film electrode provided by the embodiment of the invention comprises the following steps:
(1) mixing and dissolving 0.058g of antimony trichloride, 0.72mL of tetrabutyl titanate, 30mL of deionized water and 30mL of hydrochloric acid solution with the mass fraction of 37% to obtain a mixed solution A;
(2) cleaning the FTO conductive glass respectively with acetone, ethanol and deionized water, placing the mixed solution A obtained in the step (1) into a high-pressure reaction kettle with a polytetrafluoroethylene lining, immersing the cleaned FTO conductive glass into the mixed solution A, enabling the front side of the FTO conductive glass to face downwards, and then reacting for 6 hours at 170 ℃;
(3) and (3) after cooling, washing the FTO conductive glass treated in the step (2) with deionized water, drying at 80 ℃ for 5h, and then carrying out heat treatment in a muffle furnace at 500 ℃ for 4h to obtain the titanium dioxide film electrode.
The titanium dioxide thin film electrode prepared by the embodiment is TiO doped with antimony (Sb)
2The Sb on the nanotube array film electrode and the titanium dioxide film electrode is uniformly and orderly dispersed in the TiO
2The titanium dioxide thin film electrode has good visible light response and photocatalysis performance, good mechanical stability and long service life; the titanium dioxide thin film electrode of the embodiment can oxidize and mineralize organic pollutants by using the hydroxyl radicals with strong oxidizing property and other active oxygen generated by the titanium dioxide thin film electrode under illumination, can be used for organic wastewater, and can effectively inhibit the recombination of photon-generated carriers, promote the separation of photon-generated electrons and holes, and realize the effective utilization of the photon-generated carriers.
Example 2
As an example of the photoanode according to the present invention, as shown in fig. 2, the photoanode includes a monocrystalline silicon cell and a titanium dioxide thin film electrode as described in example 1, the monocrystalline silicon cell has a front surface and a back surface, the front surface of the monocrystalline silicon cell is smooth, the back surface of the monocrystalline silicon cell has a positive electrode and a negative electrode, the positive electrode on the back surface of the monocrystalline silicon cell and the front surface of the titanium dioxide thin film electrode as described in example 1 are connected by a lead a, the front surface of the titanium dioxide thin film electrode is a surface corresponding to the front surface of the FTO conductive glass, one end of the lead a is bonded to a top end of the front surface of the titanium dioxide thin film electrode by a conductive silver paste, and the other end of the lead is welded to the positive electrode on the back surface of the monocrystalline silicon cell, the lead B is welded to the negative electrode on the back surface of the monocrystalline silicon cell, the front surface of the monocrystalline silicon cell and the titanium dioxide thin film electrode as described, the side of the titanium dioxide thin film electrode, and the reverse side and the side of the single crystal silicon cell sheet as described in example 1 were coated with insulating epoxy resin coating, and the wire B was used for connecting an external circuit.
Fig. 3 is a performance diagram showing a light absorption curve and a light transmittance curve of the photoanode of the present embodiment, where a line 1 in fig. 3 represents the absorbance of a monocrystalline silicon cell in the photoanode, and a line 2 represents the light transmittance curve of a titanium dioxide thin film electrode in the photoanode, and it can be seen from fig. 3 that in the wavelength range of 420nm to 1200nm, the titanium dioxide thin film electrode can transmit more than 32% of light, and at the same time, the light transmitted through the titanium dioxide thin film electrode can be completely absorbed by the silicon cell, which indicates that the photoanode of the present embodiment has a good light utilization efficiency.
Example 3
The anode of the photovoltaic cell is the photo-anode described in the embodiment 2, the cathode of the photovoltaic cell is the platinum electrode, the electrolyte of the photovoltaic cell is 0.1-0.5M sodium sulfate aqueous solution, and the platinum electrode and the photo-anode described in the embodiment 2 are immersed in the 0.1-0.5M sodium sulfate aqueous solution in parallel at a certain distance.
Example 4
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) 2-chlorophenol is put into the sodium sulfate aqueous solution in the step (1) to be dissolved, and the concentration of the 2-chlorophenol is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The hydrogen generated in the embodiment is measured by gas chromatography, the organic pollutants are measured by ultraviolet-visible spectrophotometry and liquid chromatography, and the photoelectrochemistry electricity generation uses an electrochemical workstation.
Fig. 1 is a schematic view illustrating a method for degrading organic substances according to an embodiment of the present invention. In the method, the photoanode is an anode, the platinum electrode is a commercial platinum electrode as a cathode, the photoanode generates photo-generated charges under the excitation of light, and at the moment, 2-CP in the sodium sulfate aqueous solution is degraded by active species (holes, hydroxyl radicals and the like) with strong oxidizing property generated in the anode area; in the light irradiation process, photons of light penetrating through a titanium dioxide thin film electrode in the photoanode are absorbed by a monocrystalline silicon cell piece in the photoanode to generate electrons, the electrons drive the photogenerated electrons to be transmitted to the cathode through an external circuit, and H is transmitted to the cathode region
+Reduction to H
2Thereby realizing the degradation of organic pollutants and the generation of hydrogen simultaneously and generating electricity externally.
As shown in fig. 4, the removal rate and mineralization rate of 2-CP in this embodiment are shown, and it can be seen from the figure that 2-CP can be completely removed after 4h of operation, and meanwhile, the mineralization rate can also reach 32% in 4 h.
FIG. 5 shows the light intensity of the electrolytic system formed in step (1) at 100mWcm
-2The open-circuit voltage of the battery under the light irradiation condition of (1) was 2.16V, and the short-circuit current was 1.857mAcm
-2Maximum power of 967. mu. Wcm
-2。
Referring to fig. 6, the hydrogen production performance and the current density curve during hydrogen production of the method of this embodiment show that the hydrogen production rate of the present invention is 31.4μmol h
-1cm
-2The current value in the external circuit is 1.79mAcm
-2As can be seen from fig. 7, the current values did not significantly decrease or fluctuate during the hydrogen production process. The results show that the method for degrading the organic matters can well remove the organic matters in the water, and has good hydrogen production and power generation performances and good stability.
FIG. 8 is a graph showing the effect of repeatedly degrading 2-CP by the method of this embodiment, which illustrates that after 2-CP is electrolyzed in an aqueous solution of sodium sulfate, and new water containing 2-CP is repeatedly added, the degradation efficiency of 2-CP can still be maintained, and good repeatability is obtained.
Example 5
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) putting methyl orange into the sodium sulfate aqueous solution in the step (1) to be dissolved, wherein the concentration of the methyl orange is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The method for degrading organic matters has the removal rate of MO of 96.97% in 4h and the hydrogen generation rate of 32.64 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.42mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the light irradiation condition of (2), the open-circuit voltage was 2.21V, and the short-circuit current was 1.745mAcm
-2Maximum power of 894 μ Wcm
-2The result shows that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performanceCan also have good stability.
Example 6
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) putting methylene blue into the sodium sulfate aqueous solution in the step (1) to dissolve, wherein the concentration of the methylene blue is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The method for degrading organic matters has the advantages that the removal rate of methylene blue in 4h is 96.86%, and the hydrogen generation rate is 36.09 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.72mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the light irradiation condition of (2), the open-circuit voltage is 2.27V, and the short-circuit current is 1.612mAcm
-2Maximum power of 769 μ Wcm
-2The results show that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performances and good stability.
Example 7
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) putting rhodamine B into the sodium sulfate aqueous solution in the step (1) for dissolving, wherein the concentration of the rhodamine B is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The removal rate of RHB in 4h by the method for degrading organic matters in the embodiment is 95.68%, and the hydrogen generation rate is 35.86 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.36mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the condition of light irradiation, the open-circuit voltage is 2.12V, and the short-circuit current is 1.767mAcm
-2Maximum power of 882. mu. Wcm
-2The results show that the method for degrading organic matters can well remove organic matters which are difficult to degrade in water under visible light, and has good hydrogen production and power generation performances and good stability.
Example 8
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) adding atrazine into the sodium sulfate aqueous solution obtained in the step (1) for dissolving, wherein the concentration of atrazine is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The method for degrading organic matters has the removal rate of 99.8 percent of ATZ in 4h and the hydrogen generation rate of 30.95 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.26mAcm
-2And in the process of producing hydrogen said electricityThe flow value is not obviously reduced or fluctuated, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the condition of light irradiation, the open-circuit voltage is 2.23V, and the short-circuit current is 1.821mAcm
-2Maximum power of 967. mu. Wcm
-2The results show that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performances and good stability.
Example 9
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) putting ciprofloxacin into the sodium sulfate aqueous solution in the step (1) to dissolve, wherein the concentration of the ciprofloxacin is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The method for degrading organic matters in the embodiment has a CIP removal rate of 99.05% in 4h and a hydrogen generation rate of 35.1 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.38mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the light irradiation condition of (2), the open-circuit voltage was 2.18V, and the short-circuit current was 1.91mAcm
-2Maximum power of 1058. mu. Wcm
-2The results show that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performances and good stability.
Example 10
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) putting bisphenol A into the sodium sulfate aqueous solution in the step (1) to be dissolved, wherein the concentration of the bisphenol A is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo anode, and the light irradiates the titanium dioxide film electrode surface of the photo anode.
The method for degrading organic matters in the embodiment has the BPA removal rate of 96.37% in 4h and the hydrogen generation rate of 39.7 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.34mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the light irradiation condition of (2), the open-circuit voltage was 2.15V, and the short-circuit current was 1.811mAcm
-2Maximum power of 1022 μ Wcm
-2The results show that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performances and good stability.
Example 11
The method for degrading organic matters, which is an embodiment of the invention, comprises the following steps:
(1) a platinum electrode and the photo-anode described in the embodiment 2 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, and the platinum electrode and the photo-anode are connected with a lead outside the sodium sulfate aqueous solution, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) adding dichlorophenoxyacetic acid into the sodium sulfate aqueous solution in the step (1) for dissolving, wherein the concentration of the dichlorophenoxyacetic acid is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light irradiates the photo-anodeIrradiating on the titanium dioxide film electrode surface of the photo-anode.
The method for degrading organic matters in the embodiment has a removal rate of 95.46% for 2,4-D in 4h and a hydrogen generation rate of 33.5 mu mol h
-1cm
-2The current value in the external circuit is tested by an electrochemical workstation to obtain the result of 1.41mAcm
-2And the current value is not obviously reduced or fluctuated in the hydrogen production process, and the electrolytic system formed in the step (1) has the light intensity of 100mWcm
-2Under the condition of light irradiation, the open-circuit voltage is 2.22V, and the short-circuit current is 1.682mAcm
-2The maximum power is 791 mu Wcm
-2The results show that the method for degrading the organic matters can well remove the organic matters which are difficult to degrade in the water, and has good hydrogen production and power generation performances and good stability.
Comparative example 1
A method for degrading organic substances as a comparative example of the present invention, the method comprising the steps of:
(1) a platinum electrode and the titanium dioxide film electrode in the embodiment 1 are parallelly immersed in a 0.1M sodium sulfate aqueous solution at a certain distance, the platinum electrode and the photo-anode are connected outside the sodium sulfate aqueous solution through a lead, and the sodium sulfate aqueous solution is placed in a quartz reaction tank;
(2) 2-chlorophenol is put into the sodium sulfate aqueous solution in the step (1) to be dissolved, and the concentration of the 2-chlorophenol is 10 mg/L;
(3) the light intensity was 100mWcm
-2The titanium dioxide thin film electrode is irradiated with light.
The experimental result shows that the removal rate of the comparative example method to the 2-CP is only 27 percent, and the hydrogen production rate is 0 mu mol h
-1cm
-2Only 27 of example 4; open circuit voltage of 0.5V and short circuit current of 0.006mAcm
-2Maximum power of 150. mu. Wcm
-2。
Comparative example 2
A method for degrading organic substances as a comparative example of the present invention, the method comprising the steps of:
(1) parallelly immersing a platinum electrode and a monocrystalline silicon battery piece in a sodium sulfate aqueous solution of 0.1M in a certain distance, and connecting the platinum electrode and the monocrystalline silicon battery piece outside the sodium sulfate aqueous solution by using a lead, wherein the sodium sulfate aqueous solution is contained in a quartz reaction tank;
(2) 2-chlorophenol is put into the sodium sulfate aqueous solution in the step (1) to be dissolved, and the concentration of the 2-chlorophenol is 10 mg/L;
(3) the light intensity was 100mWcm
-2The light of (a) irradiates the single crystal silicon cell piece.
In the comparison method, the monocrystalline silicon cell piece is taken as the anode, the platinum electrode is taken as the cathode, and the experimental result shows that the removal rate of the 2-CP is 11 percent, and the hydrogen production rate is 17 mu mol h
-1cm
-2Only 54% of example 4; the open-circuit voltage is 2.44V, and the short-circuit current is 7.68mAcm
-2Maximum power of 967. mu. Wcm
-2。
The results of comparative example 4, comparative example 1 and comparative example 2 show that the photoanode of example 2 has better degradation efficiency and hydrogen production rate than the single crystal silicon cell or the titanium dioxide thin film electrode described in example 1 when used for degrading organic substances in water.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a titanium dioxide thin film electrode is characterized by comprising the following steps:
(1) dissolving antimony trichloride and tetrabutyl titanate in a hydrochloric acid solution to obtain a mixed solution A;
(2) immersing FTO conductive glass in the mixed solution A in a closed reaction container, and then reacting for 4-8 h at 150-180 ℃;
(3) and (3) washing the FTO conductive glass treated in the step (2) with deionized water after cooling, drying, and then carrying out heat treatment at 400-500 ℃ for 2-6 h to obtain the titanium dioxide film electrode.
2. The preparation method of the titanium dioxide thin film electrode according to claim 1, wherein the molar ratio of antimony trichloride to tetrabutyl titanate in the mixed solution A is 1: 8-9.
3. The method for preparing the titanium dioxide thin film electrode according to claim 1, wherein in the step (1), the mass concentration of the hydrochloric acid solution is 15-20%, and the concentration of antimony trichloride in the mixed solution A is 4-5 mmol/L.
4. The method for preparing the titanium dioxide thin film electrode according to claim 1, wherein in the step (2), the reaction is carried out for 6 hours at 170 ℃, in the step (3), the heat treatment is carried out for 4 hours at 500 ℃, and the closed reaction vessel is a high-pressure reaction kettle with a polytetrafluoroethylene lining.
5. The method for preparing the titanium dioxide thin film electrode according to claim 1, wherein in the step (3), the drying mode is as follows: drying for 3-7 h at 80 ℃.
6. A titania thin film electrode produced by the method as claimed in any one of claims 1 to 5.
7. A photoanode, which comprises a monocrystalline silicon cell piece and the titanium dioxide thin film electrode of claim 6, wherein a positive electrode on the reverse side of the monocrystalline silicon cell piece and a front side of the titanium dioxide thin film electrode of claim 6 are connected through a conducting wire A, the conducting wire A is connected in a welding or conductive silver adhesive bonding mode, a conducting wire B is connected to a negative electrode on the reverse side of the monocrystalline silicon cell piece, the front side of the monocrystalline silicon cell piece and the reverse side of the titanium dioxide thin film electrode of claim 6 are overlapped, and the side surface of the titanium dioxide thin film electrode of claim 6, and the reverse side and the side surface of the monocrystalline silicon cell piece are coated with insulating epoxy resin coatings.
8. A photovoltaic cell, wherein the anode of the photovoltaic cell is the photoanode of claim 7, the cathode of the photovoltaic cell is a platinum electrode, and the electrolyte of the photovoltaic cell is 0.1-0.5M sodium sulfate solution in water.
9. A method of degrading an organic matter, the method comprising the steps of:
soaking a platinum electrode and the photoanode of claim 7 in a sodium sulfate aqueous solution of 0.1-0.5M in parallel at a certain distance, and connecting the platinum electrode and the photoanode of claim 7 with a lead outside the sodium sulfate aqueous solution;
(II) putting organic pollutants into the sodium sulfate aqueous solution in the step (I);
(III) irradiating the photoanode of claim 7 with light.
10. The method according to claim 9, wherein the light in step (3) has a wavelength of 420nm to 1200nm and an intensity of 100mW cm
-2The organic matter comprises at least one of 2-chlorophenol, methyl orange, methylene blue, rhodamine B, atrazine, ciprofloxacin, bisphenol A and dichlorophenoxyacetic acid.
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| CN111755255A (en) * | 2020-07-07 | 2020-10-09 | 佛山科学技术学院 | Enhanced titanium dioxide-based thin film battery |
| CN111755255B (en) * | 2020-07-07 | 2021-07-06 | 佛山科学技术学院 | Enhanced titanium dioxide-based thin film battery |
| CN114804285A (en) * | 2022-05-23 | 2022-07-29 | 安徽农业大学 | Double-electrode mobile phase photocatalysis organic wastewater degradation device driven by sunlight |
| CN114804285B (en) * | 2022-05-23 | 2024-01-16 | 安徽农业大学 | Sunlight-driven double-electrode mobile phase photocatalytic organic wastewater degradation device |
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