CN114481205A - Copper vanadium oxide-FTO composite photoelectrode and preparation method and application thereof - Google Patents

Copper vanadium oxide-FTO composite photoelectrode and preparation method and application thereof Download PDF

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CN114481205A
CN114481205A CN202210095975.1A CN202210095975A CN114481205A CN 114481205 A CN114481205 A CN 114481205A CN 202210095975 A CN202210095975 A CN 202210095975A CN 114481205 A CN114481205 A CN 114481205A
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vanadium oxide
copper
fto
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oxide layer
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CN114481205B (en
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蒋翔
曹灵峰
汪福宪
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Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
South China University of Technology SCUT
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Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
South China University of Technology SCUT
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Abstract

The invention discloses a copper vanadium oxide-FTO composite photoelectrode and a preparation method and application thereof. The copper vanadium oxide-FTO composite photoelectrode comprises an FTO substrate, a first copper vanadium oxide layer and a second copper vanadium oxide layer which are sequentially arranged, wherein the molar ratio of Cu to V in the first copper vanadium oxide layer is 5:2, and the molar ratio of Cu to V in the second copper vanadium oxide layer is 1: 2. The preparation method of the copper vanadium oxide-FTO composite photoelectrode comprises the following steps: 1) preparing precursor solutions with different Cu and V molar ratios; 2) and sequentially depositing precursor solutions with different Cu and V molar ratios on an FTO substrate, and calcining to obtain the copper vanadium oxide-FTO composite photoelectrode. According to the invention, the copper-vanadium oxide layers with different flat band potentials are arranged on the FTO substrate, so that a Z-shaped homojunction is formed, and finally, the integral charge separation efficiency of the photoelectrode is remarkably improved.

Description

Copper vanadium oxide-FTO composite photoelectrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoelectrochemical cells, in particular to a copper vanadium oxide-FTO composite photoelectrode and a preparation method and application thereof.
Background
In recent years, the technology of hydrogen production by splitting water by a photoelectrochemical cell (PEC) has been rapidly developed and is considered to be one of the most promising approaches for producing clean energy. Photoelectrodes are the core component of light absorption and energy conversion in PEC systems, which absorb light energy to generate electron-hole pairs, which in turn separate and transport the generated charge carriers to the semiconductor-electrolyte interface for reaction. At present, common photoelectrode materials mainly include two types, i.e., transition metal oxide semiconductors and non-oxide semiconductors. The transition metal oxide semiconductor comprises BiVO4、TiO2CuO, etc., whose photoelectric properties are limited by the transport properties of carriers inside the film and at the film-substrate interface, and are more limited. The non-oxide semiconductor comprises metal sulfide, nitride, phosphide, silicon and the like, and the materials have larger photocurrent density, but are corroded by light during the photoelectrochemical reaction process, and have poor stability. In conclusion, the photoelectrode prepared by the traditional photoelectrode material has obvious defects and is difficult to completely meet the requirements of practical application.
Therefore, it is very important to develop a photoelectrode having high charge separation efficiency and excellent photoelectrochemical properties.
Disclosure of Invention
The invention aims to provide a copper vanadium oxide-FTO composite photoelectrode and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a copper vanadium oxide-FTO composite photoelectrode comprises an FTO substrate, a first copper vanadium oxide layer and a second copper vanadium oxide layer which are sequentially arranged; the molar ratio of Cu to V in the first copper vanadium oxide layer is 5: 2; the molar ratio of Cu to V in the second copper vanadium oxide layer is 1: 2.
Preferably, the thickness of the first copper vanadium oxide layer is 25nm to 750 nm.
Preferably, the thickness of the second copper vanadium oxide layer is 20nm to 600 nm.
The preparation method of the copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) dispersing copper salt and vanadium salt in a solvent to prepare a precursor solution I with the molar ratio of Cu to V being 5:2 and a precursor solution II with the molar ratio of Cu to V being 1: 2;
2) depositing the precursor solution I on an FTO substrate, and calcining to form a first copper vanadium oxide layer;
3) depositing the precursor solution II on the first copper vanadium oxide layer, calcining to form a second copper vanadium oxide layer,
and obtaining the copper vanadium oxide-FTO composite photoelectrode.
Preferably, the copper salt in step 1) is at least one of copper nitrate, copper chloride and copper acetate.
Preferably, the vanadium salt in step 1) is at least one of vanadyl acetylacetonate and ammonium metavanadate.
Preferably, the solvent in step 1) is at least one of ethanol, acetic acid and ethylene glycol.
Preferably, the FTO (F doped SnO) in the step 2)2) The substrate was ultrasonically cleaned with acetone, isopropanol and ethanol in sequence.
Preferably, the deposition in the step 2) adopts a pulse deposition mode, and the spraying time is 2-5 s and the interval is 50-60 s.
Preferably, the deposition in step 2) is carried out at a temperature of 300 ℃ to 500 ℃.
Preferably, the deposition of step 2) uses air as a carrier gas.
Preferably, the calcination in the step 2) is carried out at 350-550 ℃, and the calcination time is 1-3 h.
Preferably, the deposition in the step 3) adopts a pulse deposition mode, and the spraying time is 2 s-5 s and the interval is 50 s-60 s.
Preferably, the deposition in step 3) is carried out at a temperature of 300 ℃ to 500 ℃.
Preferably, the deposition in step 3) uses air as a carrier gas.
Preferably, the calcination in the step 3) is carried out at 350-550 ℃, and the calcination time is 1-3 h.
The photoelectrochemical cell comprises the copper vanadium oxide-FTO composite photoelectrode.
The invention has the beneficial effects that: according to the invention, the first copper vanadium oxide layer with the molar ratio of Cu to V being 5:2 and the second copper vanadium oxide layer with the molar ratio of Cu to V being 1:2 are arranged on the FTO substrate, the copper vanadium oxide layers with different flat band potentials are compounded to form a Z-shaped homojunction, so that the carrier separation efficiency in the copper vanadium oxide layer can be effectively improved, and the first copper vanadium oxide layer as a transition layer can also improve the matching degree of the energy level structures between the FTO substrate and the second copper vanadium oxide layer, so that electrons are more easily transmitted to the FTO substrate, the carrier transmission efficiency between the copper vanadium oxide layer and the FTO substrate can be improved, and finally the whole charge separation efficiency of the photoelectrode is remarkably improved.
Drawings
FIG. 1 is a Mott-Schottky curve of a copper vanadium oxide layer in a copper vanadium oxide-FTO composite photoelectrode of comparative examples 1-3.
Fig. 2 is a Tauc diagram of the copper vanadium oxide layer in the copper vanadium oxide-FTO composite photoelectrode of comparative example 1 and comparative example 3.
Fig. 3 is a plot of the linear voltammetry scans for the copper vanadium oxide-FTO composite photoelectrode of example 1, comparative example 1 and comparative example 3.
Fig. 4 is a graph showing results of internal quantum efficiency tests of the copper vanadium oxide-FTO composite photoelectrode of example 1 and comparative example 1.
Fig. 5 is a schematic diagram of the energy band structure and charge transfer of the copper vanadium oxide-FTO composite photoelectrode of example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V ultrasonic dispersion is carried out in absolute ethyl alcohol to prepare precursor solution I with Cu ion concentration of 7.5mmol/L, V and ion concentration of 3mmol/L and Cu ionPrecursor solution II with the sub-concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) sequentially and respectively ultrasonically cleaning an FTO substrate by acetone, isopropanol and ethanol for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing a precursor solution I on the FTO substrate, performing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s and 63min by using a pulse deposition mode, and calcining the FTO substrate at 500 ℃ for 2h to form a first copper-vanadium oxide layer (the thickness is 175 nm);
3) and depositing the precursor solution II on the first copper vanadium oxide layer, spraying 2s at an interval of 50s in a pulse deposition mode by using 0.2bar of air as carrier gas in the deposition process, finishing deposition after 90min, and calcining at 500 ℃ for 2h to form a second copper vanadium oxide layer (the thickness is 200nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Comparative example 1:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution with the Cu ion concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) and sequentially ultrasonically cleaning the FTO substrate by using acetone, isopropanol and ethanol respectively for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing the precursor solution on the FTO substrate, finishing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s at an interval of 90min in the deposition process, and calcining the FTO substrate at 500 ℃ for 2h to form a copper vanadium oxide layer (with the thickness of 200nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Comparative example 2:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V ultrasonic dispersion is prepared into Cu ion concentrate in absolute ethyl alcoholPrecursor solution with the ion concentration of 4.2mmol/L and the concentration of 6.3mmol/L, V;
2) and sequentially ultrasonically cleaning the FTO substrate by using acetone, isopropanol and ethanol respectively for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing the precursor solution on the FTO substrate, finishing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s at an interval of 90min in the deposition process, and calcining the FTO substrate at 500 ℃ for 2h to form a copper vanadium oxide layer (the thickness is 190nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Comparative example 3:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution with the Cu ion concentration of 7.5mmol/L, V and the ion concentration of 3 mmol/L;
2) and sequentially ultrasonically cleaning the FTO substrate by using acetone, isopropanol and ethanol respectively for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing the precursor solution on the FTO substrate, finishing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s at an interval of 90min in the deposition process, and calcining the FTO substrate at 500 ℃ for 2h to form a copper vanadium oxide layer (the thickness is 175nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
And (3) performance testing:
1) the Mott-Schottky curves (frequency of 2000Hz and amplitude of 50mV, measured in the dark using the electrochemical workstation CHI760E from chenhua instruments ltd, shanghai) of the copper vanadium oxide layer in the copper vanadium oxide-FTO composite photoelectrode of comparative examples 1 to 3 are shown in fig. 1.
As can be seen from fig. 1: the flat band potentials of the copper vanadium oxide layers in the copper vanadium oxide-FTO composite photoelectrodes of comparative examples 1 to 3 were 0.7VRHE、0.89VRHEAnd 1.2VRHE。
2) The Tauc diagrams of the copper vanadium oxide layers in the copper vanadium oxide-FTO composite photoelectrodes of comparative example 1 and comparative example 3 are shown in fig. 2.
As can be seen from fig. 2: the band gap of the copper vanadium oxide layer in the copper vanadium oxide-FTO composite photoelectrode of comparative example 1 was 1.95eV, and the band gap of the copper vanadium oxide layer in the copper vanadium oxide-FTO composite photoelectrode of comparative example 3 was 1.88 eV.
3) Linear voltammetric scan curves of the copper vanadium oxide-FTO composite photoelectrode of example 1, comparative example 1 and comparative example 3 (tested using electrochemical workstation CHI760E of Shanghai Chenghua instruments Co., Ltd., the test usingA three-electrode system, the copper vanadium oxide-FTO composite photoelectrode asA working electrode,A Pt sheet asA counter electrode, an Ag/AgCl electrode asA reference electrode,A xenon lamp CEL-HXF300 with an AM 1.5 optical filter of Beijing Zhongjingyuan scientific Co., Ltd.,A light source, and an ultraviolet illuminometer FZ-A of Beijing university Instrument Mill to correct the optical power density to 100mW/cm2The electrolyte used was borate buffer at pH 9.2) as shown in fig. 3.
As can be seen from fig. 3: compared with the copper vanadium oxide-FTO composite photoelectrode in the comparative example 1, the n-type photocurrent density of the copper vanadium oxide-FTO composite photoelectrode in the example 1 is improved by 5.6 times.
4) Internal Quantum Efficiency (IQE) test result graphs of the copper vanadium oxide-FTO composite photoelectrode of example 1 and comparative example 1 (test was performed using electrochemical workstation CHI760E of shanghai chen instruments ltd, applied voltage was 1.23V, and electrolyte solution to which Na was added was used2SO3Borate buffer of (3), Na2SO3The concentration of (2) is 0.1 mol/L) is shown in FIG. 4.
As can be seen from fig. 4: the IQE of the copper vanadium oxide-FTO composite photoelectrode of example 1 at different wavelengths (400nm to 600nm) is higher than that of the copper vanadium oxide-FTO composite photoelectrode of comparative example 1; the IQE of the copper vanadium oxide-FTO composite photoelectrode of example 1 at 400nm was 2.73%, which is 4 times that of the copper vanadium oxide-FTO composite photoelectrode of comparative example 1, indicating that the charge separation inside the copper vanadium oxide-FTO composite photoelectrode of example 1 is significantly improved.
5) The energy band structure and the charge transfer schematic of the copper vanadium oxide-FTO composite photoelectrode of example 1 are shown in fig. 5.
As can be seen from fig. 5: after the first copper vanadium oxide layer and the second copper vanadium oxide layer are compounded, the conduction band of the first copper vanadium oxide layer is higher than that of FTO, so that electrons can be smoothly transmitted to the counter electrode, and the first copper vanadium oxide layer and the second copper vanadium oxide layer can form a Z-shaped homojunction, so that the compounding of charges is reduced, the integral charge separation efficiency is improved, and the photoelectrochemical performance of the photoelectrode is improved.
Example 2:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution I with the Cu ion concentration of 7.5mmol/L, V and the ion concentration of 3mmol/L and a precursor solution II with the Cu ion concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) sequentially and respectively ultrasonically cleaning an FTO substrate by acetone, isopropanol and ethanol for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing a precursor solution I on the FTO substrate, performing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s and 9min by using a pulse deposition mode, and calcining the FTO substrate at 500 ℃ for 2h to form a first copper-vanadium oxide layer (the thickness is 25 nm);
3) and depositing the precursor solution II on the first copper vanadium oxide layer, spraying 2s at an interval of 50s for 270min in a pulse deposition mode by using 0.2bar air as carrier gas in the deposition process, and calcining at 500 ℃ for 2h to form a second copper vanadium oxide layer (the thickness is 600nm), thus obtaining the copper vanadium oxide-FTO composite photoelectrode.
Through tests, the photocurrent density of the copper vanadium oxide-FTO composite photoelectrode of the embodiment is 0.0199mA/cm2。
Example 3:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution I with the Cu ion concentration of 7.5mmol/L, V and the ion concentration of 3mmol/L and a precursor solution II with the Cu ion concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) sequentially and respectively ultrasonically cleaning an FTO substrate by acetone, isopropanol and ethanol for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 500 ℃, depositing a precursor solution I on the FTO substrate, performing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s and 270min by using a pulse deposition mode, and calcining the FTO substrate at 500 ℃ for 2h to form a first copper-vanadium oxide layer (the thickness is 750 nm);
3) and depositing the precursor solution II on the first copper vanadium oxide layer, spraying 2s at an interval of 50s in a pulse deposition mode by using 0.2bar of air as carrier gas in the deposition process, finishing deposition at 9min, and calcining at 500 ℃ for 2h to form a second copper vanadium oxide layer (the thickness is 20nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Through tests, the photocurrent density of the copper vanadium oxide-FTO composite photoelectrode of the embodiment is 0.002mA/cm2。
Example 4:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution I with the Cu ion concentration of 7.5mmol/L, V and the ion concentration of 3mmol/L and a precursor solution II with the Cu ion concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) sequentially and respectively ultrasonically cleaning an FTO substrate by acetone, isopropanol and ethanol for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 300 ℃, depositing a precursor solution I on the FTO substrate, performing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s and 63min by spraying, and calcining at 500 ℃ for 2h to form a first copper-vanadium oxide layer (the thickness is 175 nm);
3) and depositing the precursor solution II on the first copper vanadium oxide layer, spraying 2s at an interval of 50s in a pulse deposition mode by using 0.2bar of air as carrier gas in the deposition process, finishing deposition after 90min, and calcining at 500 ℃ for 2h to form a second copper vanadium oxide layer (the thickness is 200nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Through tests, the photocurrent density of the copper vanadium oxide-FTO composite photoelectrode of the embodiment is 0.0106mA/cm2。
Example 5:
a preparation method of a copper vanadium oxide-FTO composite photoelectrode comprises the following steps:
1) adding Cu (NO)3)2·3H2O and C10H14O5V, ultrasonically dispersing in absolute ethyl alcohol to prepare a precursor solution I with the Cu ion concentration of 7.5mmol/L, V and the ion concentration of 3mmol/L and a precursor solution II with the Cu ion concentration of 3.5mmol/L, V and the ion concentration of 7 mmol/L;
2) sequentially and respectively ultrasonically cleaning an FTO substrate by acetone, isopropanol and ethanol for 10min, drying the FTO substrate by using nitrogen, fixing the FTO substrate on a heating table, heating the FTO substrate to 400 ℃, depositing a precursor solution I on the FTO substrate, performing deposition by using 0.2bar of air as carrier gas in a pulse deposition mode for 2s at an interval of 50s and 63min by spraying, and calcining at 500 ℃ for 2h to form a first copper-vanadium oxide layer (the thickness is 175 nm);
3) and depositing the precursor solution II on the first copper vanadium oxide layer, spraying 2s at an interval of 50s in a pulse deposition mode by using 0.2bar of air as carrier gas in the deposition process, finishing deposition after 90min, and calcining at 500 ℃ for 2h to form a second copper vanadium oxide layer (the thickness is 200nm), thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
Through tests, the photocurrent density of the copper vanadium oxide-FTO composite photoelectrode of the embodiment is 0.0314mA/cm2。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The copper vanadium oxide-FTO composite photoelectrode is characterized in that: the copper vanadium oxide-FTO composite photoelectrode comprises an FTO substrate, a first copper vanadium oxide layer and a second copper vanadium oxide layer which are sequentially arranged; the molar ratio of Cu to V in the first copper vanadium oxide layer is 5: 2; the molar ratio of Cu to V in the second copper vanadium oxide layer is 1: 2.
2. The copper vanadium oxide-FTO composite photoelectrode of claim 1, wherein: the thickness of the first copper vanadium oxide layer is 25 nm-750 nm.
3. The copper vanadium oxide-FTO composite photoelectrode of claim 1 or 2, wherein: the thickness of the second copper vanadium oxide layer is 20 nm-600 nm.
4. The method for preparing the copper vanadium oxide-FTO composite photoelectrode as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
1) dispersing copper salt and vanadium salt in a solvent to prepare a precursor solution I with the molar ratio of Cu to V being 5:2 and a precursor solution II with the molar ratio of Cu to V being 1: 2;
2) depositing the precursor solution I on an FTO substrate, and calcining to form a first copper vanadium oxide layer;
3) and depositing the precursor solution II on the first copper vanadium oxide layer, and calcining to form a second copper vanadium oxide layer, thereby obtaining the copper vanadium oxide-FTO composite photoelectrode.
5. The method for preparing a copper vanadium oxide-FTO composite photoelectrode according to claim 4, wherein: the copper salt in the step 1) is at least one of copper nitrate, copper chloride and copper acetate.
6. The method for preparing a copper vanadium oxide-FTO composite photoelectrode according to claim 4 or 5, wherein: the vanadium salt in the step 1) is at least one of vanadyl acetylacetonate and ammonium metavanadate.
7. The method for preparing a copper vanadium oxide-FTO composite photoelectrode according to claim 4 or 5, wherein: the solvent in the step 1) is at least one of ethanol, acetic acid and glycol.
8. The method for preparing a copper vanadium oxide-FTO composite photoelectrode according to claim 4 or 5, wherein: the deposition in the step 2) adopts a pulse deposition mode, and the spraying is carried out for 2-5 s at an interval of 50-60 s; the deposition of step 2) is carried out at 300-500 ℃; the calcination in the step 2) is carried out at the temperature of 350-550 ℃, and the calcination time is 1-3 h.
9. The method for preparing a copper vanadium oxide-FTO composite photoelectrode according to claim 4 or 5, wherein: step 3), adopting a pulse deposition mode for deposition, spraying for 2-5 s at an interval of 50-60 s; the deposition in the step 3) is carried out at the temperature of 300-500 ℃; the calcination in the step 3) is carried out at the temperature of 350-550 ℃, and the calcination time is 1-3 h.
10. A photoelectrochemical cell comprising the copper vanadium oxide-FTO composite photoelectrode according to any one of claims 1 to 3.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107324441A (en) * 2017-07-07 2017-11-07 黄河科技学院 Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application
CN108389727A (en) * 2018-03-16 2018-08-10 苏州大学 Semiconductors coupling heterojunction photovoltaic pole and preparation method thereof
CN113957476A (en) * 2021-09-27 2022-01-21 山东省科学院能源研究所 Bismuth vanadate/bismuth copper oxide heterojunction catalyst and preparation method and application thereof
CN114908357A (en) * 2022-04-29 2022-08-16 山东大学 Method for producing hydrogen by adopting bismuth vanadate photoelectrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107324441A (en) * 2017-07-07 2017-11-07 黄河科技学院 Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application
CN108389727A (en) * 2018-03-16 2018-08-10 苏州大学 Semiconductors coupling heterojunction photovoltaic pole and preparation method thereof
CN113957476A (en) * 2021-09-27 2022-01-21 山东省科学院能源研究所 Bismuth vanadate/bismuth copper oxide heterojunction catalyst and preparation method and application thereof
CN114908357A (en) * 2022-04-29 2022-08-16 山东大学 Method for producing hydrogen by adopting bismuth vanadate photoelectrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
B. JANSI RANI 等: "Photoelectrochemical activity of copper vanadate nanostructures" *
林晓 等: "导电玻璃负载CuO/V2O5复合纳米纤维光电极的 制备及光电催化性能" *

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