CN114618472A - Bismuth oxide photo-anode film and preparation method thereof - Google Patents
Bismuth oxide photo-anode film and preparation method thereof Download PDFInfo
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 96
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 74
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000004528 spin coating Methods 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 claims abstract description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 2
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 abstract 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 abstract 1
- 230000003595 spectral effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
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- 239000000047 product Substances 0.000 description 4
- 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 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 230000004298 light response Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—
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- B01J35/33—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to the technical field of photocatalysis/photoelectrocatalysis, in particular to a bismuth oxide photo-anode film with adjustable spectrum absorption range and a preparation method thereof, which comprises the following steps: (1) adding Bi (NO)3)3∙5H2Dissolution of O and citric acidIn nitric acid water solution, obtaining bismuth oxycarbonate through hydrothermal reaction; (2) spin-coating the bismuth carbonate oxide mixed solution on conductive glass, and calcining to obtain a bismuth oxide thin-film electrode; (3) and placing the bismuth oxide film electrode into a reactor, wherein the bismuth oxide film electrode is a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a graphite rod electrode, the light source is visible light, and applying a bias voltage of 1.0-3.0V to the working electrode for anodic oxidation treatment to obtain the bismuth oxide photo-anode film. The invention carries out anode oxidation treatment on the bismuth oxide film to ensure that part of Bi in the bismuth oxide film is Bi3+Conversion to Bi5+The forbidden bandwidth of the bismuth oxide film is effectively reduced, and the absorption response of the bismuth oxide film to visible light is greatly widened.
Description
Technical Field
The invention relates to the technical field of photocatalysis/photoelectrocatalysis, in particular to a bismuth oxide photoanode film and a preparation method thereof.
Background
The semiconductor photoelectrocatalysis technology is an enhanced photocatalysis technology which can effectively promote electron-hole separation and utilize the synergistic action of photoelectricity, has the advantages of strong oxidation capability, high treatment efficiency, easy recycling and the like, and is one of the water treatment technologies with the most application prospect at present.
The semiconductor bismuth oxide has the characteristics of good visible light response, high valence band hole oxidation capacity, environmental friendliness and the like, and bismuth oxides with different crystal structures and compounds thereof are frequently used for the research of removing environmental pollutants through photocatalysis, and are semiconductor catalytic materials with good application prospects. However, the existing bismuth oxide and bismuth oxide composite catalytic materials mainly rely on a photocatalytic treatment technology in the field of wastewater treatment, and the catalysts have a low visible light response range, so that the improvement of the catalytic degradation pollutant activity of the materials is influenced. The method for improving the visible light absorption range of bismuth oxide mainly adopts an ion doping and semiconductor compounding method, but the visible light spectrum absorption range of the catalyst cannot be effectively expanded. Therefore, the development of the bismuth oxide material with high visible light response and adjustable spectral absorption range has important research significance for treating wastewater pollutants by using the semiconductor photoelectrocatalysis material.
Disclosure of Invention
The invention relates to a bismuth oxide photo-anode film with adjustable spectral absorption range and a preparation method thereof.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a bismuth oxide photo-anode film comprises the following steps:
(1) preparation of bismuthyl carbonate
Adding Bi (NO)3)3∙5H2Dissolving O and citric acid in a nitric acid aqueous solution, adjusting the pH to 3-5, and then carrying out hydrothermal reaction to obtain bismuth oxycarbonate;
(2) preparation of bismuth oxide film electrode
Dispersing the bismuthyl carbonate powder in the step (1) in absolute ethyl alcohol to prepare a mixed solution of 10-50 mg/mL, taking the mixed solution to spin-coat on conductive glass, heating and calcining the spin-coated conductive glass, and finally cooling to obtain a bismuth oxide thin-film electrode;
(3) preparation of bismuth oxide photo-anode film
And (3) placing the bismuth oxide film electrode in the step (2) in a reactor provided with a three-electrode working system, wherein the bismuth oxide film electrode is a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a graphite rod electrode, the light source is visible light, the distance between the bismuth oxide film working electrode and the light source is 5-30 cm, applying 1.0-3.0V bias voltage to the working electrode to carry out anodic oxidation treatment on the bismuth oxide film electrode, and the treatment time is 30-100 min, so as to obtain the bismuth oxide optical anode film.
Preferably, said Bi (NO) of step (1)3)3∙5H2The molar ratio of O to citric acid is 1: 1-1.5.
Preferably, the spin coating in the step (2) is spin coating at 1500rpm of 300-; the number of spin coating is 2-10.
Preferably, the heating and calcining temperature in the step (2) is 200-500 ℃, the heating rate of the heating and calcining is 1-10 ℃ per min, and the heat preservation time is 1-8 hours.
Preferably, the conductive glass in the step (2) is cleaned by ultrasonic treatment for 1 hour in a mixed solution of water, isopropanol and ethanol in a volume ratio of 1:1:1 before use, and then dried.
Preferably, the reactor provided with the three-electrode working system in the step (3) is a quartz reactor, and the electrolyte is 0.05-2 mol.L-1 Na2SO4An aqueous solution.
Preferably, step (1) employs NaOH solution to adjust pH.
Preferably, the hydrothermal reaction temperature in the step (1) is 150 ℃ and 250 ℃, and the hydrothermal reaction time is 10-30 hours.
A bismuth oxide photo-anode film prepared by any one of the preparation methods.
The application of the bismuth oxide photo-anode film in the field of photoelectrocatalysis degradation of pollutants.
Compared with the prior art and products, the invention has the following beneficial effects:
1. the bismuth oxide film is subjected to anodic oxidation treatment under the conditions of certain voltage and visible light irradiation, and vacancies are introduced into bismuth oxide crystal lattices to ensure that part of Bi in the bismuth oxide film3+Conversion to Bi5+The forbidden bandwidth of the bismuth oxide film is effectively reduced, and the absorption response of the bismuth oxide film to visible light is greatly widened.
2. By adjusting the magnitude of the external bias voltage in the anodic oxidation process, the valence state of bismuth ions in bismuth oxide crystal lattices can be effectively regulated and controlled to be converted from +3 valence to +5 valence, so that the movement of the optical absorption band edge of the bismuth oxide film is regulated and controlled, and the effective regulation and control of the spectral absorption range of the bismuth oxide film are realized.
Drawings
FIG. 1 is an XRD (X-ray diffraction) spectrum of a bismuth oxide film subjected to different bias oxidation treatments, which is prepared by an embodiment of the invention;
FIG. 2 is a diagram of an ultraviolet diffuse reflectance spectrum of a photo-anode film of bismuth oxide prepared according to an embodiment of the present invention and bismuth oxide after different bias oxidation treatments;
FIG. 3 is a diagram showing the activity of photocatalytic degradation of methylene blue by bismuth oxide obtained in the examples of the present invention and by a photo-anode film of bismuth oxide after oxidation treatment under different bias voltages.
Detailed Description
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention should not be construed as being limited thereto, and the insubstantial modifications and variations of the present invention as shown in the above-described summary of the invention are considered to fall within the scope of the invention by those skilled in the art.
Example 1
(1) Preparation of bismuth oxycarbonate
Weighing 2.91 g Bi (NO)3)3∙5H2O and 1.20 g of citric acid were sufficiently dissolved in 1 mol. L-1 HNO3After magnetically stirring in the aqueous solution of (1 mol. L)-1Adjusting the pH value of the NaOH solution to 4, stirring for 30min, and then carrying out hydrothermal reaction at 180 ℃ for 24 h. And after the reaction is finished, washing and drying a product to obtain the bismuthyl carbonate.
(2) Preparation of bismuth oxide film electrode
And (3) putting the FTO conductive glass into a mixed solution of water, isopropanol and ethanol in a volume ratio of 1:1:1, ultrasonically cleaning for 1 h, and airing for later use. Dispersing 0.3g of bismuthyl carbonate powder obtained in the step (1) in 10 mL of absolute ethyl alcohol, and ultrasonically dispersing in an ultrasonic cleaner to form a mixed solution of 30 mg/mL, wherein 100 muL of the mixed solution is spin-coated on conductive glass by using a spin coater at low speed of 1000 (rotation speed, rpm) for 5 s and high speed of 3000 (rotation speed, rpm) for 15 s, and the number of spin-coating times is 5. Bi obtained by spin coating2O2CO3and/FTO is heated and calcined at 360 ℃, the heating rate of the heating and calcining is 3 ℃ per min, the heat preservation time is 2 hours, and finally the bismuth oxide film electrode is obtained after natural cooling.
(3) Preparation of bismuth oxide photo-anode film with adjustable spectral range
Putting the bismuth oxide film electrode in the step (2) into a quartz reactor provided with a three-electrode working system, wherein the electrolyte is 0.5 mol.L-1 Na2SO4The water solution, the bismuth oxide film electrode as the working electrode, the reference electrode as the saturated calomel electrode, and the counter electrode as the graphiteThe rod electrode and the light source are visible light. The distance between the working electrode of the bismuth oxide film and the light source is 15cm, 1.0V bias voltage is applied to the working electrode through an electrochemical workstation, the bismuth oxide film electrode is subjected to anodic oxidation treatment for 60min, and the bismuth oxide photo-anode film with the adjustable spectral range is obtained. The XRD spectrogram and the ultraviolet-visible spectrogram of the obtained 1.0V bias pretreated bismuth oxide anode film are shown in figure 1 and 2 respectively, and the visible light absorption band edge of the bismuth oxide film is red-shifted compared with that of the bismuth oxide electrode subjected to anodic oxidation treatment, so that the effective regulation and control of the absorption range of the bismuth oxide spectrum can be realized.
Example 2
(1) Preparation of bismuth oxycarbonate
Weighing 2.91 g Bi (NO)3)3∙5H2O and 1.50 g of citric acid were sufficiently dissolved in 1 mol. L-1 HNO3After magnetically stirring in the aqueous solution of (1 mol. L)-1Adjusting the pH value of the NaOH solution to 3, stirring for 30min, and then carrying out hydrothermal reaction at 150 ℃ for 30 h. And after the reaction is finished, washing and drying a product to obtain the bismuthyl carbonate.
(2) Preparation of bismuth oxide film electrode
And (3) putting the FTO conductive glass into a mixed solution of water, isopropanol and ethanol in a volume ratio of 1:1:1, ultrasonically cleaning for 1 h, and airing for later use. Dispersing 0.1g of bismuthyl carbonate powder obtained in the step (1) in 10 mL of absolute ethyl alcohol, and ultrasonically dispersing in an ultrasonic cleaner to form 10 mg/mL of mixed solution, wherein 100 muL of mixed solution is taken each time to be spin-coated on conductive glass by using a spin coater, and the spin-coating parameters are low speed 800 (rotating speed, rpm), 5 s, high speed 4000 (rotating speed, rpm), 15 s, and the spin-coating times are 10 times. Bi obtained by spin coating2O2CO3Heating and calcining the FTO at 200 ℃, wherein the heating rate of the heating and calcining is 1 ℃ per min, the heat preservation time is 8 hours, and finally, naturally cooling to obtain the bismuth oxide film electrode.
(3) Preparation of bismuth oxide photo-anode film with adjustable spectral range
Placing the bismuth oxide film electrode in the step (2) in a quartz reactor provided with a three-electrode working systemThe electrolyte is 0.05 mol.L-1 Na2SO4The water solution, the bismuth oxide film electrode is a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a graphite rod electrode, and the light source is visible light. The distance between the working electrode of the bismuth oxide film and a light source is 15cm, 1.3V bias voltage is applied to the working electrode through an electrochemical workstation, anodic oxidation treatment is carried out on the bismuth oxide film electrode, the treatment time is 60min, and the bismuth oxide photo-anode film with the adjustable spectral range is obtained. The XRD spectrogram and the ultraviolet-visible spectrogram of the obtained 1.3V bias pretreated bismuth oxide anode film are shown in figures 1 and 2 respectively, and the visible light absorption band edge of the bismuth oxide film is red-shifted compared with that of the bismuth oxide electrode subjected to anodic oxidation treatment, so that the effective regulation and control of the spectral absorption range of the bismuth oxide can be realized.
Example 3
(1) Preparation of bismuth oxycarbonate
Weighing 2.91 g Bi (NO)3)3∙5H2O and 2.0 g of citric acid were sufficiently dissolved in 1 mol. L-1HNO3After magnetically stirring, the mixture was stirred with 1 mol. L-1Adjusting the pH value of the NaOH solution to 5, stirring for 30min, and then carrying out hydrothermal reaction at 200 ℃ for 10 h. And after the reaction is finished, washing and drying a product to obtain the bismuthyl carbonate.
(2) Preparation of bismuth oxide film electrode
And (3) putting the FTO conductive glass into a mixed solution of water, isopropanol and ethanol in a volume ratio of 1:1:1, ultrasonically cleaning for 1 h, and airing for later use. Dispersing 0.5g of bismuthyl carbonate powder obtained in the step (1) in 10 mL of absolute ethyl alcohol, and ultrasonically dispersing in an ultrasonic cleaner to form 50 mg/mL of mixed solution, wherein 100 muL of mixed solution is taken each time to be spin-coated on conductive glass by using a spin coater, and the spin-coating parameters are low speed 800 (rotating speed, rpm), 5 s, high speed 4000 (rotating speed, rpm), 15 s, and the spin-coating times are 2 times. Bi obtained by spin coating2O2CO3and/FTO is heated and calcined at 360 ℃, the heating rate of the heating and calcining is 8 ℃ per min, the heat preservation time is 8 hours, and finally the bismuth oxide film electrode is obtained after natural cooling.
(3) Preparation of bismuth oxide photo-anode film with adjustable spectral range
Putting the bismuth oxide film electrode in the step (2) into a quartz reactor provided with a three-electrode working system, wherein the electrolyte is 0.1 mol.L-1 Na2SO4The water solution, the bismuth oxide film electrode is a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a graphite rod electrode, and the light source is visible light. The distance between the working electrode of the bismuth oxide film and the light source is 10cm, 1.8V bias voltage is applied to the working electrode through an electrochemical workstation, and the bismuth oxide film electrode is subjected to anodic oxidation treatment for 100min, so that the bismuth oxide photo-anode film with the adjustable spectral range is obtained. The XRD spectrogram and the ultraviolet-visible spectrogram of the obtained 1.8V bias pretreated bismuth oxide anode film are shown in figure 1 and 2 respectively, and the visible light absorption band edge of the bismuth oxide film is obviously red-shifted compared with that of the bismuth oxide electrode subjected to anodic oxidation treatment, so that the effective regulation and control of the spectral absorption range of the bismuth oxide can be realized.
Example 4
(1) Photoelectrocatalysis activity test of prepared film photoanode
Methylene blue is taken as a target pollutant for photoelectrocatalysis degradation, the concentration is 10 mg.L < -1 >, and the electrolyte is 0.5 mol.L-1 Na2SO4Taking the bismuth oxide electrode prepared in the examples 1-3 as a working electrode, the calomel electrode as a reference electrode and the graphite rod as a counter electrode. The tests were carried out in a 100 mL self-made quartz reactor. The method comprises the following steps of using a 500W xenon lamp light source as a light source, filtering ultraviolet light below 420 nm by using a light filter, applying a voltage of 1.0V to a working electrode by using a three-electrode system, carrying out a photoelectrocatalytic degradation activity test on a bismuth oxide photoanode, sampling once every 20 min by using a liquid-transferring gun, carrying out rapid centrifugation on a sample, and taking a supernatant to test the dye concentration on an ultraviolet-visible spectrophotometer. The test result is shown in figure 3, and it can be seen that compared with the bismuth oxide film photoanode which is not subjected to anodic oxidation treatment, the activity of the bismuth oxide electrode subjected to different bias anodic oxidation treatment for photoelectrocatalytic degradation of methylene blue is effectively improved, wherein the catalytic activity of the bismuth oxide film electrode subjected to anodic oxidation pretreatment of 1.8V is the highest, and the activity is improved by about 20% compared with the bismuth oxide photoanode which is not subjected to anodic oxidation treatment.
Claims (10)
1. The preparation method of the bismuth oxide photo-anode film is characterized by comprising the following steps of:
preparation of bismuth oxycarbonate
Adding Bi (NO)3)3∙5H2Dissolving O and citric acid in a nitric acid aqueous solution, adjusting the pH to 3-5, and then carrying out hydrothermal reaction to obtain bismuth oxycarbonate;
preparation of bismuth oxide film electrode
Dispersing the bismuthyl carbonate powder in the step (1) in absolute ethyl alcohol to prepare a mixed solution of 10-50 mg/mL, taking the mixed solution to spin-coat on conductive glass, heating and calcining the spin-coated conductive glass, and finally cooling to obtain a bismuth oxide thin-film electrode;
(3) preparation of bismuth oxide photo-anode film
And (3) placing the bismuth oxide film electrode in the step (2) in a reactor provided with a three-electrode working system, wherein the bismuth oxide film electrode is a working electrode, the reference electrode is a saturated calomel electrode, the counter electrode is a graphite rod electrode, the light source is visible light, the distance between the bismuth oxide film working electrode and the light source is 5-30 cm, applying 1.0-3.0V bias voltage to the working electrode to carry out anodic oxidation treatment on the bismuth oxide film electrode, and the treatment time is 30-100 min, so as to obtain the bismuth oxide optical anode film.
2. The method according to claim 1, wherein said Bi (NO) of step (1)3)3∙5H2The molar ratio of O to citric acid is 1: 0.5-2.
3. The method as claimed in claim 1, wherein the spin coating in step (2) is performed at 1500rpm of 300-; the number of spin coating is 2-10.
4. The preparation method as claimed in claim 1, wherein the heating calcination temperature in step (2) is 200-500 ℃, the heating rate of the heating calcination is 1-10 ℃ per min, and the holding time is 1-8 hours.
5. The preparation method according to claim 1, wherein the conductive glass in the step (2) is ultrasonically cleaned for 1 hour in a mixed solution of water, isopropanol and ethanol in a volume ratio of 1:1:1 before use, and then is dried.
6. The method according to claim 1, wherein the reactor equipped with the three-electrode working system in the step (3) is a quartz reactor, and the electrolyte is 0.05 to 2 mol-L-1 Na2SO4An aqueous solution.
7. The method according to claim 1, wherein the pH in step (1) is adjusted with NaOH solution.
8. The preparation method as claimed in claim 1, wherein the hydrothermal reaction temperature in step (1) is 150 ℃ and 250 ℃ and the hydrothermal reaction time is 10-30 hours.
9. A bismuth oxide photo-anode film produced by the production method according to any one of claims 1 to 8.
10. The use of the bismuth oxide photoanode film of claim 9, wherein the bismuth oxide photoanode film is used in the field of photoelectrocatalytic degradation of pollutants.
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