CN109308982B - Preparation method of co-modified copper bismuthate nanorod photocathode - Google Patents

Preparation method of co-modified copper bismuthate nanorod photocathode Download PDF

Info

Publication number
CN109308982B
CN109308982B CN201811217738.8A CN201811217738A CN109308982B CN 109308982 B CN109308982 B CN 109308982B CN 201811217738 A CN201811217738 A CN 201811217738A CN 109308982 B CN109308982 B CN 109308982B
Authority
CN
China
Prior art keywords
cubi
nanorod
photocathode
drying
fto
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811217738.8A
Other languages
Chinese (zh)
Other versions
CN109308982A (en
Inventor
马德琨
马春艳
余文缘
黄少铭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wenzhou University
Original Assignee
Wenzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wenzhou University filed Critical Wenzhou University
Priority to CN201811217738.8A priority Critical patent/CN109308982B/en
Publication of CN109308982A publication Critical patent/CN109308982A/en
Application granted granted Critical
Publication of CN109308982B publication Critical patent/CN109308982B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

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

Preparation method of co-modified copper bismuthate nanorod photocathode
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.
CN201811217738.8A 2018-10-18 2018-10-18 Preparation method of co-modified copper bismuthate nanorod photocathode Active CN109308982B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811217738.8A CN109308982B (en) 2018-10-18 2018-10-18 Preparation method of co-modified copper bismuthate nanorod photocathode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811217738.8A CN109308982B (en) 2018-10-18 2018-10-18 Preparation method of co-modified copper bismuthate nanorod photocathode

Publications (2)

Publication Number Publication Date
CN109308982A CN109308982A (en) 2019-02-05
CN109308982B true CN109308982B (en) 2020-11-06

Family

ID=65224369

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811217738.8A Active CN109308982B (en) 2018-10-18 2018-10-18 Preparation method of co-modified copper bismuthate nanorod photocathode

Country Status (1)

Country Link
CN (1) CN109308982B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110201676A (en) * 2019-06-21 2019-09-06 西北工业大学 A kind of bismuthic acid Copper thin film that inlaying no ligand quantum dot, preparation method and application
CN110205638B (en) * 2019-07-08 2021-01-08 辽宁大学 Z-shaped CuBi2O4/SnO2Photoelectric cathode film and preparation method and application thereof
CN111482150B (en) * 2020-04-22 2022-07-19 上海市普陀区人民医院(上海纺织第一医院) Visible light response all-copper-based series photoelectric catalytic device and preparation method thereof
CN113308711B (en) * 2021-05-26 2022-08-26 绍兴文理学院 Preparation method and application of F-doped CBO nanorod array photocathode material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120315523A1 (en) * 2011-06-09 2012-12-13 Michael Pozin Electrochemical cells with improved spiral-wound electrode assembly
CN104762634B (en) * 2015-03-18 2018-03-16 中国科学院理化技术研究所 Optical electro-chemistry decomposes aquatic products hydrogen, the optoelectronic pole for producing oxygen and its preparation and application
US10683218B2 (en) * 2015-07-29 2020-06-16 The Regents Of The University Of California Z-scheme microbial photoelectrochemical system (MPS) for wastewater-to-chemical fuel conversion

Also Published As

Publication number Publication date
CN109308982A (en) 2019-02-05

Similar Documents

Publication Publication Date Title
CN109308982B (en) Preparation method of co-modified copper bismuthate nanorod photocathode
Jang et al. Photoelectrochemical water splitting with p‐type metal oxide semiconductor photocathodes
Tang et al. Smoothing surface trapping states in 3D coral-like CoOOH-wrapped-BiVO4 for efficient photoelectrochemical water oxidation
Lin et al. Plasmonic Ag@ Ag 3 (PO 4) 1− x nanoparticle photosensitized ZnO nanorod-array photoanodes for water oxidation
Huang et al. Promoting charge carrier utilization by integrating layered double hydroxide nanosheet arrays with porous BiVO4 photoanode for efficient photoelectrochemical water splitting
Yang et al. One dimensional SnO2 NRs/Fe2O3 NTs with dual synergistic effects for photoelectrocatalytic reduction CO2 into methanol
Li et al. MoS2 nanosheet/ZnO nanowire hybrid nanostructures for photoelectrochemical water splitting
CN112410819A (en) Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof
CN110331416B (en) CoOOH nanosheet modified Fe2O3Preparation method and application of composite photo-anode
Sari et al. Synthesis and characterizations of Cu2O/Ni (OH) 2 nanocomposite having a double co-catalyst for photoelectrochemical hydrogen production
CN111774057B (en) High-performance heterojunction material Fe2O3/CuO photoelectrode film and preparation method and application thereof
Wei et al. Cooperation effect of heterojunction and co-catalyst in BiVO 4/Bi 2 S 3/NiOOH photoanode for improving photoelectrochemical performances
Qiao et al. Molybdenum disulfide/silver/p-silicon nanowire heterostructure with enhanced photoelectrocatalytic activity for hydrogen evolution
Jeong et al. Improvement of CuO photostability with the help of a BiVO4 capping layer by preventing self-reduction of CuO to Cu2O
CN110965073B (en) WO containing defects3Preparation method of photoelectrode
CN111482150B (en) Visible light response all-copper-based series photoelectric catalytic device and preparation method thereof
CN111962090B (en) Ti3C2-MXene modified alpha-iron oxide photoelectrode and preparation method thereof
CN110344096B (en) AgSbS2Sensitized TiO2Composite membrane material and preparation and application thereof
CN111509243A (en) Application of CNTs modified BiOCl/ZnO heterojunction nano-array photo-anode in photocatalytic fuel cell
CN109972149B (en) Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film
CN111525142A (en) CNTs modified BiOCl/ZnO heterojunction nano-array photoanode for photocatalytic fuel cell
CN107268020A (en) A kind of Ta3N5The preparation method and Ta of film3N5The application of film
CN108993469B (en) ZnO quantum dot TiO2Nanosheet composite structure and preparation method thereof
Qiao et al. Enhancement of photoelectrochemical Hydrogen evolution of p-type silicon nanowires array by loading MoS2
CN111378961B (en) Gold nanoparticle-loaded lanthanum ferrite film and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant