CN109308982B - Preparation method of co-modified copper bismuthate nanorod photocathode - Google Patents
Preparation method of co-modified copper bismuthate nanorod photocathode Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 150000001879 copper Chemical class 0.000 title claims description 11
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- 238000000034 method Methods 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 239000004332 silver Substances 0.000 claims abstract description 22
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- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
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- 101710134784 Agnoprotein Proteins 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000000576 coating method Methods 0.000 abstract 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/12—Manufacture of electrodes or electrode systems of photo-emissive cathodes; of secondary-emission electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a co-repair methodThe preparation method of the copper bismuthate nanorod photocathode comprises the following steps: (1) CuBi is hydrothermally synthesized by using abundant and cheap bismuth source and copper source under alkaline condition2O4A nanorod; (2) adopts an ion-alternative physical adsorption method to load silver ions on CuBi2O4On the nano-rod; (3) the CuBi is formed by using FTO conductive glass as a substrate and adopting a dripping coating method2O4Ag film, annealing treatment by CVD method; (4) and (4) peeling and transferring the material to a second piece of FTO glass by adopting a particle transfer technology, and carrying out ultrasonic treatment. Then preparing nitrogen-doped carbon quantum dots and silver co-modified CuBi by physically adsorbing the nitrogen-doped carbon quantum dots2O4And (3) a nanorod photocathode. The photocathode prepared by the method shows good photoelectrocatalysis activity and visible light response characteristic under the irradiation of visible light, improves the stability, and can be effectively applied to the field of hydrogen production by water decomposition of photoelectrocatalysis.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to nitrogen-doped carbon quantum dot and silver co-modified CuBi2O4A method for preparing a nano-rod photocathode.
Background
Environmental pollution and energy crisis have become a necessary threat to human development, and there is an urgent need to find green and sustainable alternative energy. Titanium dioxide (TiO) was discovered in Honda and Taenikao in 19722) Since photoelectrode produces hydrogen in photoelectrochemical cell (PEC), water is a focus material for energy sustainability through the use of decomposition as a hydrogen generation source, especially the water decomposition of the PEC can effectively convert solar energy into sustainable green energy source-hydrogen gas, which is recognized as an effective way to solve environmental pollution and crisis. Nevertheless, TiO2The wide energy gap (3.2eV) makes it possible to absorb only ultraviolet rays, accounting for about 1.4% of solar energy, resulting in low light utilization efficiency. Therefore, it is important to develop a narrow bandgap semiconductor material with efficient visible light activity.
Element-rich metal oxide p-type semiconductor CuBi2O4Due to its uniqueThe properties are considered to be an effective material for water splitting applications, such as a sufficiently narrow direct band gap (1.8eV), a very positive onset potential and low cost. Assuming that all energy is absorbed and utilized by 100% efficiency, the maximum theoretical photocurrent density under AM1.5 irradiation can reach 19.7-29.0mA/cm2. Unfortunately, CuBi2O4Poor photoelectric conversion efficiency due to poor charge carrier transport and poor reaction kinetics, and unstable self-photoelectricity corrosion when the material is in contact with an electrolyte solution, which limit the application and competitiveness of the material in the water decomposition of PEC.
Improvement of CuBi2O4The photoelectrode has the best solar-chemical energy conversion efficiency, can be realized by nano structure design, selective element doping, heterojunction formation with certain semiconductors or supported cocatalyst, and the implementation of the strategies facilitates the rapid separation and transportation of photogenerated electrons to the surface for proton reduction, so that CuBi in the electrolyte solution can be improved2O4The light conversion efficiency of (1). However, these results cannot be compared with their theoretical values. How to obtain CuBi with higher photoelectric conversion efficiency and photoelectric stability in a simple and cheap manner2O4Photocathodes remain a challenge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a co-modified copper bismuthate nanorod photocathode, nitrogen-doped carbon quantum dots and nano-silver co-doping can effectively inhibit the surface recombination of electrons and holes and improve the reaction kinetics, and the co-doped carbon quantum dots and the nano-silver can be combined with naked CuBi2O4Compared with a photoelectrode, the PEC performance is greatly improved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a co-modified copper bismuthate nanorod photocathode comprises the following steps:
step S1, adding 2.42g Bi (NO)3)3·5H2O、0.6g Cu(NO3)3·5H2Adding O and 0.87g NaOH into 40mL of deionized water in sequence, and stirring for 3 hours to dissolve to obtain a solution;
s2, transferring the solution obtained in the step S1 to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 24 hours at 180 ℃, after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, centrifugally separating solid products in the solution, repeatedly and alternately washing the solid products with absolute ethyl alcohol and high-purity water for three times, and then drying the solid products in a drying box at 60 ℃ to obtain CuBi2O4A nanorod;
step S3, weighing 30mg of CuBi prepared in step S22O4The nanorods were added to 10mL of absolute ethanol, followed by different volumes of 0.05M AgNO3Stirring the solution for 3h until the solution is absorbed and balanced, and drying the solution in a drying box at the temperature of 60 ℃ to obtain a powdery product;
step S4, putting the FTO glass into acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning the FTO glass, taking the FTO glass out, cleaning the FTO glass with absolute ethyl alcohol, and carrying out N2Drying;
step S5, dispersing 20mg of the powdered product obtained in step S3 in 0.1mL of absolute ethanol to form a suspension, then dripping the suspension on FTO glass treated by the method of step S4, drying the FTO glass in a drying oven at 60 ℃, and then adopting a CVD method in N2Annealing for 4h at 450 ℃ in atmosphere to obtain Ag-doped CuBi2O4A nanorod;
step S6, the Ag doped CuBi prepared in the step S5 is mixed by carbon adhesive tape2O4The nanorods are peeled off from the FTO glass and transferred to another FTO glass treated by the method of step S4, and then subjected to ultrasonic treatment in water to remove excess Ag/CuBi2O4Obtaining the FTO/CuBi material from the nano-rod material2O4a/Ag photocathode;
step S7, the FTO/CuBi prepared in the step S62O4Putting the/Ag photocathode into 10mL of absolute ethyl alcohol, adding nitrogen-doped carbon quantum dot solutions with different volumes, stirring for 3h until the adsorption is balanced, drying in a drying oven at 60 ℃, covering the peripheral area with epoxy resin during drying, and obtaining the nitrogen-doped carbon quantum dot and silver co-modified CuBi after drying2O4And (3) a nanorod photocathode.
Further, in step S2, the inner container volume of the teflon-lined autoclave was 50 mL.
Further, in step S3, the 0.05M AgNO3The volume of solution added was 0.4 mL.
Further, in step S5, the specific method for applying the suspension drop on the FTO glass processed by the method of step S4 is: 0.05mL of the suspension was pipetted onto the FTO glass treated by the method of step S4.
Further, in step S6, the ultrasonic power of the ultrasonic treatment is 60W, and the ultrasonic time is 15 min.
Further, in step S7, the volume of the nitrogen-doped carbon quantum dot solution added is 0.6 mL.
The invention has the beneficial effects that:
the method of the invention uses abundant and cheap bismuth source and copper source to hydrothermally synthesize CuBi under alkaline condition2O4Nano-rods, and then loading silver ions on CuBi by adopting an ion-alternative physical adsorption method2O4On the nano-rod; then, the FTO conductive glass is used as a substrate, and a dripping method is adopted to form CuBi2O4Annealing the/Ag film by a CVD method, peeling and transferring the material to a second piece of FTO glass by a particle transfer technology, and carrying out ultrasonic treatment. Finally, preparing nitrogen-doped carbon quantum dots and silver co-modified CuBi by physically adsorbing the nitrogen-doped carbon quantum dots2O4And (3) a nanorod photocathode.
Nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared by the method2O4Nanorod photocathode (FTO/CuBi)2O4Ag/N-CQD) shows good photoelectrocatalysis activity and visible light response characteristic under the irradiation of visible light, the stability is improved, and the method can be effectively applied to the field of hydrogen production by photoelectrocatalysis water decomposition.
Drawings
FIG. 1 shows that nitrogen-doped carbon quantum dots and silver co-modified CuBi prepared in example 1 of the present invention2O4SEM image of nanorod photocathode.
FIG. 2 shows CuBi2O4TEM image of/Ag/N-CQD composite.
FIG. 3 is CuBi2O4Nanorod and CuBi2O4Ag material and CuBi2O4Schematic diagram of XRD diffraction pattern of/Ag/N-CQD composite material.
FIG. 4 shows CuBi2O4Nanorod and CuBi2O4Ag material, nitrogen-doped carbon quantum dot prepared in embodiment 1 of the invention and silver co-modified CuBi2O4Solid diffuse reflectance spectrum of nanorod photocathode.
FIG. 5 shows CuBi2O4Nanorod and CuBi2O4Ag material, CuBi2O4Fluorescence spectrum of/Ag/N-CQD composite material.
FIG. 6 shows FTO/CuBi2O4、FTO/CuBi2O4Ag photoelectrode and nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared in embodiment 1 of the invention2O4Impedance spectrum of nanorod photocathode.
FIG. 7 shows FTO/CuBi2O4、FTO/CuBi2O4Ag photoelectrode and nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared in embodiment 1 of the invention2O4MOtt-SchOttky curve of nanorod photocathode.
FIG. 8 shows FTO/CuBi2O4、FTO/CuBi2O4Ag photoelectrode, FTO/CuBi2O4N-CQD photoelectrode and nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared in embodiment 1 of the invention2O4Photoelectric property diagram of nanorod photocathode.
FIG. 9 shows FTO/CuBi2O4、FTO/CuBi2O4Ag photoelectrode and nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared in embodiment 1 of the invention2O4Current-time curve of nanorod photocathode.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that the present embodiment is based on the technical solution, and the detailed implementation and the specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a preparation method of a co-modified copper bismuthate nanorod photocathode, which comprises the following steps:
step S1, adding 2.42g Bi (NO)3)3·5H2O、0.6g Cu(NO3)3·5H2Adding O and 0.87g NaOH into 40mL of deionized water in sequence, and stirring for 3 hours to dissolve to obtain a solution;
s2, transferring the solution obtained in the step S1 to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 24 hours at 180 ℃, after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, centrifugally separating solid products in the solution, repeatedly and alternately washing the solid products with absolute ethyl alcohol and high-purity water for three times, and then drying the solid products in a drying box at 60 ℃ to obtain CuBi2O4A nanorod;
step S3, weighing 30mg of CuBi prepared in step S22O4The nanorods were added to 10mL of absolute ethanol, followed by different volumes of 0.05M AgNO3Stirring the solution for 3h until the solution is absorbed and balanced, and drying the solution in a drying box at the temperature of 60 ℃ to obtain a powdery product;
step S4, putting the FTO glass into acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning the FTO glass, taking the FTO glass out, cleaning the FTO glass with absolute ethyl alcohol, and carrying out N2Drying;
step S5, dissolving 20mg of the powdered product obtained in step S3 in 0.1mL of absolute ethanol to form a suspension, then dripping the suspension on FTO glass treated by the method of step S4, drying the FTO glass in a drying oven at 60 ℃, and then performing CVD on the FTO glass in an N atmosphere2Annealing for 4h at 450 ℃ in atmosphere to obtain Ag-doped CuBi2O4A nanorod;
step S6, the Ag doped CuBi prepared in the step S5 is mixed by carbon adhesive tape2O4The nanorods are peeled off from the FTO glass and transferred to another FTO glass treated by the method of step S4, and then subjected to ultrasonic treatment in water to remove excess Ag/CuBi2O4Obtaining the FTO/CuBi material from the nano-rod material2O4a/Ag photocathode;
step S7, step CFTO/CuBi prepared from S62O4Putting the/Ag photocathode into 10mL of absolute ethyl alcohol, adding nitrogen-doped carbon quantum dot solutions with different volumes, stirring for 3h until the adsorption is balanced, drying in a drying oven at 60 ℃, covering the peripheral area with epoxy resin during drying, and obtaining the nitrogen-doped carbon quantum dot and silver co-modified CuBi after drying2O4And (3) a nanorod photocathode.
Further, in step S2, the inner container volume of the teflon-lined autoclave was 50 mL.
Further, in step S3, the 0.05M AgNO3The optimal volume of solution added is 0.4 mL.
Further, in step S5, the specific method for applying the suspension drop on the FTO glass processed by the method of step S4 is: 0.05mL of the suspension was pipetted onto the FTO glass treated by the method of step S4.
Further, in step S6, the ultrasonic power of the ultrasonic treatment is 60W, and the ultrasonic time is 15 min.
Further, in step S7, the optimal addition volume of the nitrogen-doped carbon quantum dot solution is 0.6 mL.
FIG. 1 shows that the nitrogen-doped carbon quantum dots and silver co-modified CuBi prepared by the method of this embodiment2O4SEM image of nanorod photocathode. From FIG. 1, it can be seen that nitrogen-doped carbon quantum dots and silver co-modified CuBi2O4The nanorod photoelectric cathode is a nanorod with the length of about 2 microns and the width of about 300 nm.
FIG. 2 shows CuBi2O4TEM image of/Ag/N-CQD composite. From fig. 2, it can be seen that the surface of the nanorod is loaded with nitrogen-doped carbon quantum dots.
As can be seen from the X-ray diffraction pattern shown in FIG. 3, the co-modified product CuBi2O4Ag/N-CQD, product CuBi modified only with Ag2O4/Ag、CuBi2O4The X-ray diffraction patterns of (A) are similar, with a slight shift.
It can be seen from the diffuse reflection of UV shown in FIG. 4 that the light-absorbing material is compatible with CuBi2O4In contrast, the co-modified product CuBi2O4Ag/N-CQD and CuBi product modified only with Ag2O4The visible light absorption of/Ag is not enhanced significantly.
Analysis from the fluorescence spectrum result shown in FIG. 5, with CuBi2O4Compared with CuBi which is a product only modifying Ag2O4The fluorescence intensity of Ag is weakened, and the doping of Ag is favorable for charge separation. And co-modifying the product CuBi2O4The fluorescence intensity of/Ag/N-CQD is the weakest, which indicates that the nitrogen-doped carbon quantum dot can effectively separate photon-generated carriers.
From the analysis of the impedance spectrum results shown in FIG. 6, FTO/CuBi2O4Photoelectrode and FTO/CuBi2O4Compared with Ag photoelectrode, the co-modified product nitrogen-doped carbon quantum dot and silver co-modified CuBi prepared by the method of the embodiment2O4Nanorod photocathode (FTO/CuBi)2O4/Ag/N-CQD) impedance was minimal, indicating that co-modification improves charge transfer efficiency.
Analysis from the results of the MOtt-SchOttky curve shown in FIG. 7, together with FTO/CuBi2O4Comparison of photoelectrode, FTO/CuBi2O4Ag photoelectrode, co-modified product nitrogen-doped carbon quantum dot prepared by the method of the embodiment and silver co-modified CuBi2O4The slopes of the curves corresponding to the nanorod photocathodes are increased, which indicates that the co-modification is beneficial to improving the carrier concentration.
Example 2
This example describes the nitrogen-doped carbon quantum dots and silver co-modified CuBi prepared in example 12O4The nano-rod photocathode is used for carrying out a photoelectrocatalysis performance test, and the test conditions are as follows: a standard three-electrode system was used, with a saturated calomel electrode and a Pt wire electrode as the reference and counter electrodes, respectively. AM1.5 solar simulator (100 mW/cm)2) As an illumination source. Taking 85mL of 0.5ML phosphate buffer solution in a photoelectric reaction cell, setting the distance between a light source and a reaction system to be 10cm, and irradiating from the front side to have the distance of 0.5cm2The electrolyte exposes an area of the working electrode. The potential range is-0.6-0.5V and the scanning speed is 10mV s-1. The electrode potential is based on the RHE standard, E(RHE)＝E(SCE)+0.059*6.6+0.242。
Analysis from the photoelectric property diagram shown in FIG. 8, and FTO/CuBi2O4Photoelectrode and FTO/CuBi2O4Compared with Ag photoelectrode, the nitrogen-doped carbon quantum dot prepared in example 1 and silver co-modified CuBi2O4The nanorod photocathode shows higher photocurrent, which indicates that the co-modification increases the charge transfer efficiency and the carrier separation efficiency, and improves the capability of decomposing water to produce hydrogen.
Analysis from the current-time curve results shown in FIG. 9, with FTO/CuBi2O4Photoelectrode and FTO/CuBi2O4Compared with Ag photoelectrode, the nitrogen-doped carbon quantum dot prepared in example 1 and silver co-modified CuBi2O4The nanorod photocathode shows good stability.
Various changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present claims.
Claims (6)
1. A preparation method of a co-modified copper bismuthate nanorod photocathode is characterized by comprising the following steps:
step S1, adding 2.42g Bi (NO)3)3·5H2O、0.6g Cu(NO3)3·5H2Adding O and 0.87g NaOH into 40mL of deionized water in sequence, and stirring for 3 hours to dissolve to obtain a solution;
s2, transferring the solution obtained in the step S1 to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 24 hours at 180 ℃, after the reaction is finished, cooling the high-pressure reaction kettle to room temperature, centrifugally separating solid products in the solution, repeatedly and alternately washing the solid products with absolute ethyl alcohol and high-purity water for three times, and then drying the solid products in a drying box at 60 ℃ to obtain CuBi2O4A nanorod;
step S3, weighing 30mg of CuBi prepared in step S22O4The nanorods were added to 10mL of absolute ethanol, followed by different volumes of 0.05M AgNO3Stirring the solution for 3 hours toCarrying out adsorption balance, and drying in a drying oven at 60 ℃ to obtain a powdery product;
step S4, putting the FTO glass into acetone, absolute ethyl alcohol and deionized water in sequence, ultrasonically cleaning the FTO glass, taking the FTO glass out, cleaning the FTO glass with absolute ethyl alcohol, and carrying out N2Drying;
step S5, dispersing 20mg of the powdered product obtained in step S3 in 0.1mL of absolute ethanol to form a suspension, then dripping the suspension on FTO glass treated by the method of step S4, drying the FTO glass in a drying oven at 60 ℃, and then adopting a CVD method in N2Annealing for 4h at 450 ℃ in atmosphere to obtain Ag-doped CuBi2O4A nanorod;
step S6, the Ag doped CuBi prepared in the step S5 is mixed by carbon adhesive tape2O4The nanorods are peeled off from the FTO glass and transferred to another FTO glass treated by the method of step S4, and then subjected to ultrasonic treatment in water to remove excess Ag/CuBi2O4Obtaining the FTO/CuBi material from the nano-rod material2O4a/Ag photocathode;
step S7, the FTO/CuBi prepared in the step S62O4Putting the/Ag photocathode into 10mL of absolute ethyl alcohol, adding nitrogen-doped carbon quantum dot solutions with different volumes, stirring for 3h until the adsorption is balanced, drying in a drying oven at 60 ℃, covering the peripheral area with epoxy resin during drying, and obtaining the nitrogen-doped carbon quantum dot and silver co-modified CuBi after drying2O4And (3) a nanorod photocathode.
2. The method for preparing a co-modified copper bismuthate nanorod photocathode according to claim 1, wherein in step S2, the inner container of the polytetrafluoroethylene-lined high-pressure reaction kettle has a volume of 50 mL.
3. The method for preparing the co-modified copper bismuthate nanorod photocathode of claim 1, wherein in step S3, the 0.05M AgNO is added3The volume of solution added was 0.4 mL.
4. The method for preparing the co-modified copper bismuthate nanorod photocathode according to claim 1, wherein in the step S5, the specific method for applying the suspension drop on the FTO glass treated by the method in the step S4 is as follows: 0.05mL of the suspension was pipetted onto the FTO glass treated by the method of step S4.
5. The method for preparing the co-modified copper bismuthate nanorod photocathode according to claim 1, wherein in step S6, the ultrasonic power of ultrasonic treatment is 60W, and the ultrasonic time is 15 min.
6. The method for preparing the co-modified copper bismuthate nanorod photocathode of claim 1, wherein in the step S7, the volume of the nitrogen-doped carbon quantum dot solution is 0.6 mL.
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