CN113809199A - Laser-induced preparation of nano bismuth surface plasma enhanced composite photoelectrode - Google Patents
Laser-induced preparation of nano bismuth surface plasma enhanced composite photoelectrode Download PDFInfo
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- RLWWKAGRZATJDC-UHFFFAOYSA-L tris(2-methylphenyl)bismuth(2+);dichloride Chemical compound CC1=CC=CC=C1[Bi](Cl)(Cl)(C=1C(=CC=CC=1)C)C1=CC=CC=C1C RLWWKAGRZATJDC-UHFFFAOYSA-L 0.000 claims description 2
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- FRCOHGLXOJLAFR-UHFFFAOYSA-N cadmium;pentane-2,4-dione Chemical compound [Cd].CC(=O)CC(C)=O FRCOHGLXOJLAFR-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical group [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
The laser-induced nano bismuth-three-dimensional porous graphene plasma-enhanced composite photoelectrode preparation method based on the bismuth ion-doped polysulfone polymer film is developed and adopts a laser-induced preparation mode. Firstly, dissolving a bismuth ion precursor required by preparing laser-induced nano bismuth into a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), then adding a polysulfone polymer, continuously performing magnetic stirring until the solution is dissolved, rotationally coating the obtained viscous solution on the surface of indium tin oxide conductive glass, drying in vacuum, evaporating the solvent, namely forming a bismuth ion-polysulfone polymer composite membrane on the surface of the indium tin oxide conductive glass, and utilizing CO2Scanning the surface of the bismuth ion-polyether sulfone composite film by an infrared laser engraving machine to prepare and form nano bismuth-three-dimensional polyThe porous graphene plasma reinforced composite photoelectrode. The laser-induced nano bismuth-three-dimensional porous graphene plasma reinforced composite photoelectric material can be used for expanding the photoresponse range of semiconductors.
Description
Technical Field
The invention relates to a novel synchronous and in-situ laser induction preparation method of a nano metal bismuth surface plasma resonance enhanced composite photoelectrode and application thereof in expanding the photoresponse range of semiconductors.
Background
Photoelectrochemistry (PEC) is widely applied to the aspects of photoelectrocatalysis, environmental management, biosensing and the like, and has the advantages of high response speed, high sensitivity and the like. In a PEC sensor, reasonable design and preparation of a photoelectrode with high photoelectric conversion efficiency play a crucial role in improving PEC sensing analysis performance, and with the rapid development of nanotechnology and nanomaterial science, a large number of photoelectric active materials are applied to the preparation of the photoelectrode, wherein the formation of a heterostructure is one of important ways for improving the efficiency of the photoelectrode. In this regard, noble metal (e.g., gold, silver, and platinum) nanostructures with unique Surface Plasmon Resonance (SPR) properties are considered to be ideal materials for constructing highly sensitive PEC sensors. The noble metal nano structure can not only absorb visible light and infrared light, but also promote the effective separation of electron-hole pairs in a semiconductor under the action of SPR.
At present, metallic bismuth (Bi)0) The nanostructure enhances the metal-semiconductor composite photocatalyst/photoelectrode at SPR, such as Bi0-metal oxide, Bi0-BiOX and Bi0-g-C3N4, has received increasing attention in its construction and has been successfully used in the fields of photocatalysis and PEC sensing. Compared with the traditional noble metal, the metal Bi0Excellent electronic performance, low cost and easy obtaining. Thus, Bi0Have become an ideal alternative to traditional noble metals to improve the analytical performance of PEC sensors. Graphene has excellent electrical/thermal conductivity and excellent optical/mechanical properties, and has become the most popular matrix material in the aspects of SPR enhanced photocatalyst/photoelectrode preparation, photocatalysis, PEC sensing and the like. Graphene can not only significantly improve the stability of photoactive materials, but also improve the visible light PEC performance of photoelectrodes. However, the conventional preparation method of the graphene composite material based on the liquid phase reaction usually requires harsh conditions such as high temperature/high pressure and long reaction time, and thus the large-scale preparation and application of the composite photoelectrode are greatly limited. In recent years, a laser direct writing technology for directly preparing a graphene composite electrode on a polyimide film by using carbon dioxide laser is receiving more and more attention, the reaction conditions are mild (normal temperature and normal pressure), large-scale batch preparation is easy to realize, and in-situ and solid-phase conversion of three-dimensional porous graphene on various substrates is realized. The obtained laser-induced graphene (LIG) has high conductivity, large surface area and good mechanical stability. Due to the excellent properties, the laser-induced graphene is widely researched in the fields of electrocatalysis, electric energy storage, gas/tension/pressure sensors and the like. Furthermore, recent studies have shown that CO2Laser irradiation can synthesize various metal-graphene nanocomposite materials.Thus, LIG is Bi0The simple preparation of graphene composite photoelectrode and the application thereof in novel SPR enhanced PEC sensing provide a new idea.
In addition to direct use as photosensitive materials, the metals Bi0It can also be coupled with other wider bandgap semiconductors (e.g., CdS) to extend their light absorption range to near infrared light, thereby enhancing their PEC performance. Therefore, it is imperative to develop a simple and stable new method for preparing the efficient SPR enhanced nano bismuth-graphene composite photoelectrode. Aiming at the requirements, a novel preparation method of the laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photo-electrode is developed. The polysulfone polymer is used as a carbon source, and a bismuth ion doped polysulfone polymer film on the surface of the indium tin oxide conductive glass is synchronously converted into an SPR (surface plasmon resonance) enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode with excellent photo-induced electrochemical performance in situ.
Disclosure of Invention
The invention aims to provide a preparation method of a laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photo-electrode based on a bismuth ion doped polysulfone polymer film, and the laser-induced nano bismuth is utilized to expand the photoresponse range of a wide band gap semiconductor.
The technical scheme of the invention is as follows
A preparation method of a laser-induced SPR (surface plasmon resonance) -enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode is shown in figure 1, and adopts a laser-induced synchronous preparation mode, firstly, a bismuth ion precursor required for preparing laser-induced metal bismuth is dissolved into N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), then, polysulfone polymer is added to be continuously stirred magnetically until the bismuth ion precursor is dissolved, the obtained viscous solution is coated on the surface of indium tin oxide conductive glass in a rotating mode, after vacuum drying, a bismuth ion-polysulfone polymer composite membrane is formed on the surface of the indium tin oxide conductive glass, and CO is utilized to form the bismuth ion-polysulfone polymer composite membrane on the surface of the indium tin oxide conductive glass2The laser engraving machine engraves a pre-designed photoelectrode pattern on the surface of the bismuth ion-polysulfone composite membrane to prepare and form SPR enhanced nano bismuth-three-dimensional porous graphene and the likeAn ion-enhanced composite photoelectrode.
The precursor of bismuth ions required by the preparation of the laser-induced nano bismuth is bismuth nitrate pentahydrate, tri-o-tolyl bismuth dichloride or triphenyl bismuth.
The polysulfone polymer is polysulfone, polyethersulfone or polyphenylsulfone.
The preparation method of the laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode comprises the following steps:
step 1, adding a bismuth ion precursor (0.12-0.18 g) required for preparing laser-induced nano bismuth into 20-30 mL of a mixed solution of DMF and DMSO, and magnetically stirring to completely dissolve the bismuth ion precursor;
step 2, adding 2.0-3.0 g of polysulfone polymer into the solution obtained in the step 1 for 3-5 times (with the time interval of 20-30 minutes), and continuously stirring until a bismuth ion-containing polysulfone polymer solution with certain viscosity is formed;
step 3, spin-coating the bismuth ion-containing polysulfone polymer solution synthesized in the step 2 to the surface of the cleaned indium tin oxide conductive glass according to a certain amount, and forming a uniform bismuth ion-containing polysulfone polymer solution film on the surface of the indium tin oxide conductive glass, wherein the spin-coating speed is 2000-3000 r/min, and the spin-coating time is 80-100 s;
step 4, drying the indium tin oxide conductive glass modified by the bismuth ion-containing polysulfone polymer solution film obtained in the step 3 at 75-100 ℃ for 1-2 h in vacuum, and volatilizing the solvent obtained in the solution, namely preparing the bismuth ion-doped polysulfone polymer film on the surface of the indium tin oxide conductive glass;
step 5, cooling the bismuth ion doped polysulfone polymer film obtained in the step 4 to room temperature, and adding CO2Working platform of laser engraving machine using CO2The surface of the bismuth ion doped polysulfone polymer film is scanned by laser, and the bismuth ion doped polysulfone polymer film on the surface of the indium tin oxide conductive glass is directly, in-situ and synchronously converted into the SPR enhanced nano bismuth-three-dimensional porous graphene composite nano material.
The preparation method of the laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode is characterized by comprising the following steps: the laser power is 4.0-4.8W, the laser engraving speed is 250 mm/s, the laser engraving resolution is 600-1200, and the laser defocusing distance is 0.2-0.4 cm.
Based on the SPR enhanced nano bismuth-three-dimensional porous graphene composite material, the SPR enhanced nano bismuth-semiconductor-three-dimensional porous graphene ternary composite optical electrode prepared for expanding the optical response range of the wide band gap semiconductor comprises the following steps:
step 1, sequentially adding a bismuth ion precursor (0.12-0.18 g) required for preparing laser-induced nano bismuth and a metal ion precursor (0.09-0.13 g) required for preparing a laser-induced semiconductor into 20-30 mL of a DMF (dimethyl formamide) + DMSO mixed solution, and magnetically stirring to completely dissolve the precursors;
step 2, adding 2.0-3.0 g of polysulfone polymer into the solution obtained in the step 1 for 3-5 times (with the time interval of 20-30 minutes), and continuously stirring to form a solution containing the metal ion polysulfone polymer with certain viscosity;
step 3, spin-coating the solution of the polysulfone polymer containing the metal ions synthesized in the step 2 on the surface of the indium tin oxide conductive glass which is cleaned, and forming a uniform film of the polysulfone polymer containing the metal ions on the surface of the indium tin oxide conductive glass, wherein the spin-coating speed is 2000-3000 r/min, and the spin-coating time is 80-100 s;
step 4, drying the indium tin oxide conductive glass modified by the metal ion-containing polysulfone polymer solution film obtained in the step 3 at the temperature of 75-100 ℃ for 1-2 hours in vacuum, and volatilizing a solvent to obtain a metal ion-doped polysulfone polymer film on the surface of the indium tin oxide conductive glass;
step 5, cooling the metal ion doped polysulfone polymer film obtained in the step 4 to room temperature, and adding CO2Working platform of laser engraving machine using CO2The method comprises the steps of scanning the surface of a metal ion doped polysulfone polymer film by laser, and directly, in situ and synchronously converting the metal ion doped polysulfone polymer film on the surface of indium tin oxide conductive glass into an SPR (surface plasmon resonance) enhanced nano bismuth-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.
The preparation method of the laser-induced SPR enhanced nano bismuth-semiconductor-three-dimensional porous graphene ternary composite photoelectrode is characterized by comprising the following steps: the laser power is 4.0-4.8W, the laser engraving speed is 250 mm/s, the laser engraving resolution is 600-1200, and the laser defocusing distance is 0.2-0.4 cm.
The metal ion precursor required for preparing the laser-induced semiconductor is acetylacetone titanium, acetylacetone cadmium, acetylacetone lead, lead acetate and tungsten chloride.
The preparation principle of the laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode is as follows:
during the laser engraving process, due to CO2The photo-thermal effect of the laser can increase the local instantaneous temperature of the bismuth ion doped polysulfone polymer film to nearly 3000 ℃, and sp in the polysulfone polymer film3Conversion of hybrid carbon to sp2And hybridizing carbon, and finally highly graphitizing the polysulfone polymer film containing a large number of benzene ring structures to generate the graphene. The violent graphitization process is accompanied by the release of gases such as water vapor and nitrogen to form a three-dimensional porous structure. In addition, bismuth ions are reduced into a metal bismuth nanostructure under the reducing atmosphere generated by laser induction, so that the SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode is prepared and formed.
Compared with the prior art, the invention has the following characteristics:
the invention provides a preparation method of a laser-induced SPR (surface plasmon resonance) enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode, which has the following characteristics compared with the traditional photoelectrode preparation method:
(1) the novel laser-induced preparation method can be used for preparing and generating the SPR reinforced nano bismuth-three-dimensional porous graphene composite nano material on the surface of the indium tin oxide conductive glass in situ and synchronously, has the characteristics of simple and rapid operation steps, accurate and controllable electrode area and strong universality, and can realize mass preparation.
(2) According to the novel laser-induced preparation method, the bismuth ion-doped polysulfone polymer film is directly converted into the SPR (surface plasmon resonance) -enhanced nano bismuth-three-dimensional porous graphene composite nano material in a solid phase manner at normal temperature and normal pressure, the reaction is rapid, the condition is mild, and the cost is low.
(3) The laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode disclosed by the invention has rapid photocurrent response and higher photocurrent output to ultraviolet-visible-near infrared light.
(4) The laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode prepared by the invention has high stability, can realize continuous and stable output of photocurrent within 10000s, has good repeatability, can be repeatedly used for more than 50 times, and can be stably stored for more than 12 months at room temperature.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photo-electrode.
Detailed Description
Embodiment 1. preparation of laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photo-electrode:
preparing a bismuth ion-containing polysulfone solution: adding 0.8g of bismuth nitrate pentahydrate into 5ml of DMF + DMSO, stirring by magnetic force until the bismuth nitrate pentahydrate is completely dissolved, then adding 2.5 g of polyethersulfone for 5 times (the time interval is 2 hours), and continuously stirring until a solution of polyethersulfone containing bismuth ions with certain viscosity is formed; spin-coating the solution to the surface of the cleaned indium tin oxide conductive glass according to a certain amount, wherein the spin-coating speed is 1000 r/min, the spin-coating time is 60 s, forming a uniform bismuth ion-containing polyether sulfone solution film on the surface of the indium tin oxide conductive glass, and performing vacuum drying on the obtained bismuth ion-containing polyether sulfone solution film at the temperature of 80 ℃ for 2 h to volatilize the solvent, so that the bismuth ion-doped polyether sulfone film is prepared on the surface of the indium tin oxide conductive glass;
preparing an SPR (surface plasmon resonance) enhanced nano bismuth-three-dimensional porous graphene composite photo-electrode by laser induction: cooling the obtained bismuth ion doped polyether sulfone film modified indium tin oxide conductive glass to room temperature, and adding CO2Laser cutting carving machine working platform using CO2The surface of the bismuth ion doped polyether sulfone film is scanned by laser, and the bismuth ion doped polyether sulfone film on the surface of the indium tin oxide conductive glass is directly converted into a nano bismuth-three-dimensional porous graphene composite material in situ to form the SPR reinforced composite photoelectrode. The laser engraving parameters were as follows: laserThe power was 4.0W, the laser engraving speed was 166 mm/s, the laser engraving resolution was 1200, and the laser defocus distance was 0.3 cm.
Embodiment 2. preparation of laser-induced SPR enhanced nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite photo-electrode:
preparing a polyethersulfone solution containing bismuth ions and cadmium ions: firstly, 0.8g of bismuth nitrate pentahydrate and 0.56g of cadmium acetylacetonate are added into 5mL of DMF + DMSO mixed solution, the mixture is stirred by magnetic force to be completely dissolved, then 2.5 g of polyethersulfone is added into the mixture by 5 times (the time interval is 2 hours), and the mixture is continuously stirred to form the polyethersulfone solution with certain viscosity and containing bismuth ions and cadmium ions;
preparing indium tin oxide conductive glass modified by bismuth ion and cadmium ion polyether sulfone films: spin-coating the polyether sulfone solution containing bismuth ions and cadmium ions to the surface of the cleaned indium tin oxide conductive glass according to a certain amount, wherein the spin-coating speed is 1200 r/min, the spin-coating time is 50 s, forming a uniform polyether sulfone solution film containing bismuth ions and cadmium ions on the surface of the indium tin oxide conductive glass, and carrying out vacuum drying on the obtained polyether sulfone solution film containing bismuth ions and cadmium ions at the temperature of 80 ℃ for 2 h to volatilize a solvent, so that the polyether sulfone film doped with bismuth ions and cadmium ions is prepared on the surface of the indium tin oxide conductive glass;
preparing an SPR (surface plasmon resonance) enhanced nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite photo-electrode by laser induction: cooling the obtained bismuth ion and cadmium ion doped polyether sulfone film modified indium tin oxide conductive glass to room temperature, and adding CO2Laser cutting carving machine working platform using CO2Laser scans the surface of the bismuth ion and cadmium ion doped polyether sulfone film, and the bismuth ion and cadmium ion doped polyether sulfone film on the surface of the indium tin oxide conductive glass is directly converted into a nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite material in situ to form the SPR reinforced composite photoelectrode. The laser engraving parameters were as follows: the laser power is 4.1W, the laser engraving speed is 170 mm/s, the laser engraving resolution is 1200, and the laser defocusing distance is 0.4 cm.
Claims (5)
1. Bismuth ion doped polysulfone polymer filmA preparation method of a laser-induced SPR (surface plasmon resonance) -enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode adopts a laser-induced synchronous preparation mode, firstly, bismuth ion precursors required for preparing laser-induced nano bismuth are dissolved into N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), then, polysulfone polymers are added to be continuously stirred magnetically until the bismuth ion precursors are dissolved, the obtained viscous solution is coated on the surface of indium tin oxide conductive glass in a rotating mode, after vacuum drying, a bismuth ion-polysulfone polymer composite membrane is formed on the surface of the indium tin oxide conductive glass, and CO is utilized to form the bismuth ion-polysulfone polymer composite membrane2The infrared laser engraving machine engraves a pre-designed photoelectrode pattern on the surface of the bismuth ion-polyether sulfone composite membrane, and then the SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode is prepared. The laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode can widen the photoresponse range of cadmium sulfide semiconductors.
2. The method for preparing the laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode as claimed in claim 1, wherein the method comprises the following steps: the bismuth ion precursor required for preparing the laser-induced nano bismuth is bismuth nitrate pentahydrate, tri-o-tolyl bismuth dichloride or triphenyl bismuth.
3. The preparation method for preparing the SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode as claimed in claim 1 is characterized by comprising the following steps:
step 1, adding a bismuth ion precursor (0.12-0.18 g) required for preparing laser-induced nano bismuth into 20-30 mL of a mixed solution of DMF and DMSO, and magnetically stirring to completely dissolve the bismuth ion precursor;
step 2, adding 2.0-3.0 g of polysulfone polymer into the solution obtained in the step 1 for 3-5 times (with the time interval of 20-30 minutes), and continuously stirring to form a bismuth ion-containing polysulfone polymer solution with certain viscosity;
step 3, spin-coating the bismuth ion-containing polysulfone polymer solution synthesized in the step 2 to the surface of the cleaned indium tin oxide conductive glass, and forming a uniform bismuth ion-containing polysulfone polymer solution film on the surface of the indium tin oxide conductive glass, wherein the spin-coating speed is 2000-3000 r/min, and the spin-coating time is 80-100 s;
step 4, carrying out vacuum heat preservation on the indium tin oxide conductive glass modified by the bismuth ion-containing polysulfone polymer solution film obtained in the step 3 at the temperature of 75-100 ℃ for 1-2 h, so that a solvent is volatilized, and thus the bismuth ion-doped polysulfone polymer film is prepared on the surface of the indium tin oxide conductive glass;
step 5, cooling the bismuth ion doped polysulfone polymer film obtained in the step 4 to room temperature, and adding CO2Working platform of laser engraving machine using CO2The surface of the bismuth ion doped polysulfone polymer film is scanned by laser, and the bismuth ion doped polysulfone polymer film on the surface of the indium tin oxide conductive glass is directly, in-situ and synchronously converted into the SPR enhanced nano bismuth-three-dimensional porous graphene composite nano material.
4. The SPR enhanced nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite optical electrode prepared by adopting the SPR enhanced nano bismuth-three-dimensional porous graphene composite material based on the claim 1 and expanding the photoresponse range of cadmium sulfide comprises the following steps:
step 1, sequentially adding a bismuth ion precursor (0.12-0.18 g) required for preparing laser-induced nano bismuth and a cadmium ion precursor (0.09-0.13 g) required for preparing laser-induced cadmium sulfide into 20-30 mL of DMF (dimethyl formamide) + DMSO mixed solution, and magnetically stirring to completely dissolve the bismuth ion precursor and the cadmium ion precursor;
step 2, adding 2.0-3.0 g of polysulfone polymer into the solution obtained in the step 1 for 3-5 times (the time interval is 20-30 minutes), and continuously stirring to form a polysulfone polymer solution with certain viscosity and containing cadmium ions and bismuth ions;
step 3, spin-coating the polysulfone polymer solution containing the cadmium ions and the bismuth ions synthesized in the step 2 on the surface of the cleaned indium tin oxide conductive glass to form a uniform polysulfone polymer solution film containing the cadmium ions and the bismuth ions on the surface of the indium tin oxide conductive glass, wherein the spin-coating speed is 2000-3000 r/min, and the spin-coating time is 80-100 s;
step 4, drying the indium tin oxide conductive glass modified by the polysulfone polymer solution film containing the cadmium ions and the bismuth ions obtained in the step 3 in vacuum at the temperature of 75-100 ℃ for 1-2 hours to volatilize the solvent, namely preparing the polysulfone polymer film doped with the cadmium ions and the bismuth ions on the surface of the indium tin oxide conductive glass;
step 5, cooling the cadmium ion and bismuth ion doped polysulfone polymer film obtained in the step 4 to room temperature, and adding CO2Working platform of laser engraving machine using CO2The laser scans the surface of the polysulfone polymer film doped with cadmium ions and bismuth ions, and the cadmium ions and the bismuth ions on the surface of the indium tin oxide conductive glass are directly, in situ and synchronously converted into the SPR enhanced nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite photoelectrode.
5. The laser-induced SPR enhanced nano bismuth-three-dimensional porous graphene composite photoelectrode according to claim 1 and the laser-induced SPR enhanced nano bismuth-cadmium sulfide-three-dimensional porous graphene ternary composite photoelectrode according to claim 3, wherein the preparation method comprises the following steps: the laser power is 4.0-4.8W, the laser engraving speed is 250 mm/s, the laser engraving resolution is 600-1200, and the laser defocusing distance is 0.2-0.4 cm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107203052A (en) * | 2017-05-05 | 2017-09-26 | 柯剑 | Electro-deposition display module and preparation method thereof |
| US20190051898A1 (en) * | 2017-08-11 | 2019-02-14 | University Of Maryland, College Park | Bismuth composite nanoparticle anodes, methods of making same, and uses thereof |
| CN110203964A (en) * | 2019-05-05 | 2019-09-06 | 青岛农业大学 | A kind of preparation of induced with laser metal sulfide/three-dimensional porous graphene complex light electrode |
| CN110578069A (en) * | 2019-10-24 | 2019-12-17 | 青岛大学 | Preparation method of metal and alloy nanocrystalline |
| WO2020081409A1 (en) * | 2018-10-18 | 2020-04-23 | Global Graphene Group, Inc. | Porous graphene particulate-protected anode active materials for lithium batteries |
-
2020
- 2020-06-17 CN CN202010552379.2A patent/CN113809199A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107203052A (en) * | 2017-05-05 | 2017-09-26 | 柯剑 | Electro-deposition display module and preparation method thereof |
| US20190051898A1 (en) * | 2017-08-11 | 2019-02-14 | University Of Maryland, College Park | Bismuth composite nanoparticle anodes, methods of making same, and uses thereof |
| WO2020081409A1 (en) * | 2018-10-18 | 2020-04-23 | Global Graphene Group, Inc. | Porous graphene particulate-protected anode active materials for lithium batteries |
| CN110203964A (en) * | 2019-05-05 | 2019-09-06 | 青岛农业大学 | A kind of preparation of induced with laser metal sulfide/three-dimensional porous graphene complex light electrode |
| CN110578069A (en) * | 2019-10-24 | 2019-12-17 | 青岛大学 | Preparation method of metal and alloy nanocrystalline |
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