阅读说明：本技术 一种激光诱导电催化剂-半导体-三维多孔石墨烯三元复合光电极的制备 (Preparation of laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode ) 是由 不公告发明人 于 2019-11-10 设计创作，主要内容包括：一种激光诱导电催化剂-半导体-三维多孔石墨烯三元复合光电极的制备本发明公开了一种激光诱导电催化剂-半导体-三维多孔石墨烯复合光电极的制备方法,它采用激光诱导制备方式。首先将制备激光诱导电催化剂所需的金属离子前驱体与制备激光诱导半导体所需的金属离子前驱体溶解至N,N-二甲基甲酰胺中,然后加入聚砜类聚合物持续进行磁力搅拌直至溶解,将得到的粘性溶液旋转涂膜至氧化铟锡导电玻璃表面,经真空加热后,在氧化铟锡导电玻璃表面形成金属离子-聚砜类聚合物复合膜,利用CO-2红外激光(l=10.64 mm)雕刻机,将预先设计好的光电极图案雕刻至金属离子-聚醚砜复合膜的表面,即制备形成电催化剂-半导体-三维多孔石墨烯三元复合光电极。(The invention discloses a preparation method of a laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene composite photoelectrode, which adopts a laser-induced preparation mode. Firstly, dissolving a metal ion precursor required by preparing a laser-induced electrocatalyst and a metal ion precursor required by preparing a laser-induced semiconductor into N, N-dimethylformamide, then adding a polysulfone polymer, continuously performing magnetic stirring until the polysulfone polymer is dissolved, rotationally coating the obtained viscous solution on the surface of indium tin oxide conductive glass, heating in vacuum, and then coating the indium tin oxide conductive glass on the surface of the indium tin oxide conductive glassForming a metal ion-polysulfone polymer composite film by using CO 2 And (3) engraving a pre-designed photoelectrode pattern to the surface of the metal ion-polyether sulfone composite membrane by using an infrared laser (l =10.64 mm) engraving machine, so as to prepare and form the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.)

1. A laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode is prepared by adopting a laser-induced synchronous preparation mode, firstly dissolving a metal ion precursor required by preparing a laser-induced electrocatalyst and a metal ion precursor required by preparing a laser-induced semiconductor into N, N-Dimethylformamide (DMF), then adding a polysulfone polymer, continuously performing magnetic stirring until the metal ion precursor and the metal ion precursor are dissolved, rotationally coating the obtained viscous solution on the surface of indium tin oxide conductive glass, and forming gold on the surface of the indium tin oxide conductive glass after vacuum heatingBelongs to an ion-polysulfone polymer composite membrane and utilizes CO₂And (3) engraving a pre-designed photoelectrode pattern to the surface of the metal ion-polyether sulfone composite membrane by using an infrared laser (l =10.64 mm) engraving machine, so as to prepare and form the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.

2. And finally, detecting the concentration of the glucose in the alkaline glucose sample solution by using the photoelectrode.

3. The method for preparing the laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode according to claim 1, wherein the method comprises the following steps: the metal ion precursor required by the preparation of the laser-induced semiconductor is cadmium acetylacetonate or cadmium nitrate.

4. The metal ion precursor needed for preparing the laser-induced electrocatalyst is nickel acetylacetonate or nickel nitrate.

5. The preparation method for preparing the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode as claimed in claim 1 is characterized by comprising the following steps:

step 1, sequentially adding a metal ion precursor (0.12-0.18 g) required for preparing a laser induced photocatalyst and a metal ion precursor (0.09-0.13 g) required for preparing a laser induced semiconductor into 20-30 mL of DMF solution, and magnetically stirring to completely dissolve the metal ion precursor and the metal 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 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, carrying out vacuum heat preservation on 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 h, so that a solvent is volatilized, and thus the metal ion-doped polysulfone polymer film is prepared 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 electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.

6. The preparation method of the laser electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode according to claim 1, wherein: the laser power is 4.0-4.8 w, the laser engraving speed is 166-250 mm/s, the laser engraving resolution is 600-1200, and the laser defocusing distance is 0.2-0.4 cm.

Technical Field

The invention relates to a preparation method of a novel laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.

Background

Photoelectrochemistry (photoelectrochemistry) has a wide application range, and is particularly applied to photoelectrocatalysis, environmental management, biosensing and the like. Glucose, a high-energy biomass and an important small molecule biomarker, plays a crucial role in fuel cell development, wastewater treatment, clinical diagnosis and food industry for efficient oxidation and highly sensitive detection. At present, it has been reported that PEC glucose oxidation/detection systems mostly use glucose oxidase or a single semiconductor as a photocatalyst, greatly limiting their practical applications. In order to overcome this problem, researchers have developed an enzyme-free composite photoelectrode that includes a semiconductor material as a light energy absorber and an attached electrocatalyst as a reaction site for electrocatalytic oxidation of glucose, which greatly improves the oxidation efficiency and detection sensitivity of glucose. When excited by light, the semiconductor can effectively absorb light energy to generate electron-hole pairs, and the electro-catalyst can accept holes from the semiconductor, so that the glucose oxidation reaction is catalyzed. As is well known, metal nickel or oxides and hydroxides thereof show high-efficiency electrocatalytic performance on glucose in an alkaline medium, so that the metal nickel or oxides and hydroxides thereof have wide attention in the fields of glucose electrooxidation and electroanalysis, in order to realize more efficient PEC glucose oxidation and detection, the prepared photoelectrode has high conductivity to promote photoinduced charge transfer and large surface area to expose more active sites and contact more glucose molecules, and the conventional preparation method of the electrocatalyst-semiconductor composite photoelectrode is relatively complicated and complex in steps and high in cost, so that the patent develops a novel preparation method of the laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode aiming at the problem, and the polysulfone polymer is simultaneously used as a carbon source and a sulfur source to dope a metal complex on the surface of indium tin oxide conductive glass with a polysulfone polymer film in situ Synchronously converted into an electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite material to form a composite photoelectrode with excellent photo-induced electrochemical performance. The method is simple, stable and strong in universality, and can realize mass preparation.

Disclosure of Invention

The invention aims to provide a photoelectrode preparation method for synchronously preparing an electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite nanomaterial by laser induction.

The technical scheme of the invention is as follows

A preparation method of a laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode is shown in figure 1Firstly, dissolving a metal ion precursor required by preparing a laser-induced electrocatalyst and a metal ion precursor required by preparing a laser-induced semiconductor into N, N-Dimethylformamide (DMF), then adding a polysulfone polymer, continuously carrying out magnetic stirring until the precursors are dissolved, rotationally coating the obtained viscous solution on the surface of indium tin oxide conductive glass, heating in vacuum, forming a metal ion-polysulfone polymer composite film on the surface of the indium tin oxide conductive glass, and utilizing CO₂And (3) engraving a pre-designed photoelectrode pattern to the surface of the metal ion-polyether sulfone composite membrane by using an infrared laser (l =10.64 mm) engraving machine, so as to prepare and form the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.

The metal ion precursor required for preparing the laser-induced semiconductor is cadmium acetylacetonate or cadmium nitrate.

The metal ion precursor required for preparing the laser-induced electrocatalyst is nickel acetylacetonate or nickel nitrate.

The polysulfone polymer is polysulfone, polyethersulfone or polyphenylsulfone.

The preparation method of the laser induced photocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode comprises the following steps:

step 1, sequentially adding a metal ion precursor (0.12-0.18 g) required for preparing a laser induced photocatalyst and a metal ion precursor (0.09-0.13 g) required for preparing a laser induced semiconductor into 20-30 mL of DMF solution, and magnetically stirring to completely dissolve the metal ion precursor and the metal 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 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, carrying out vacuum heat preservation on 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 h, so that a solvent is volatilized, and thus the metal ion-doped polysulfone polymer film is prepared 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 electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite nano material.

The preparation method of the laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene composite photoelectrode is characterized by comprising the following steps of: the laser power is 4.0-4.8 w, the laser engraving speed is 166-250 mm/s, the laser engraving resolution is 600-1200, and the laser defocusing distance is 0.2-0.4 cm.

The preparation principle of the laser induced photocatalyst-semiconductor-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 metal 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. Meanwhile, sulfur element in the polysulfone polymer is reduced into S by carbon heat under the condition of existence of metal ions^2-And the CdS semiconductor nano-particles are combined with cadmium ions to form CdS semiconductor nano-particles which are uniformly attached to the three-dimensional porous graphene, and in addition, nickel ions are reduced into a metallic nickel elementary substance electrocatalyst by reducing atmosphere generated by laser induction, so that the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode is prepared and formed. In the composite photo-electrode, semiconductor cadmium sulfide is used as a light energy absorberThe separation of electrons and holes generated by light excitation can lead the electrons in the conduction band out efficiently by the graphene, thereby effectively avoiding the recombination of the electrons and the holes and improving the photoelectric conversion efficiency. Oxidation of electrocatalyst metallic nickel to Ni (OH) by holes in valence band under basic conditions₂，Ni(OH)₂Can be further oxidized by sufficient holes to nio (oh). In this case, NiO (OH) is an electrocatalytically active center, and glucose is oxidized to a glucose ester and reduced to Ni (OH) itself₂And realizing the circulating photoelectrocatalysis oxidation of the glucose. .

Compared with the prior art, the invention has the following characteristics:

the invention provides a preparation method of a laser-induced electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode, which has the following characteristics compared with the traditional photoelectrode preparation method:

(1) the novel laser-induced preparation method can synchronously prepare and generate the electrocatalyst-semiconductor-three-dimensional porous graphene composite photoelectric material on the surface of the indium tin oxide conductive glass, has the characteristics of simple and rapid operation steps, accurate and controllable electrode area and strong universality, and can realize mass preparation.

(2) The electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode has high photoelectrocatalysis oxidation efficiency on glucose under an alkaline condition.

(3) The electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode prepared by laser direct writing has high stability and 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 an electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode.

Detailed Description

Example 1 preparation of an electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode:

preparing a polyether sulfone solution containing cadmium ions and nickel ions: adding 0.45 g of cadmium acetylacetonate and 0.32 g of nickel acetylacetonate into 5 mL of DMF, carrying out magnetic stirring to completely dissolve the cadmium acetylacetonate and the nickel acetylacetonate, adding 2.5 g of polyethersulfone for 5 times (with the time interval of 2 hours), and continuously stirring to form a polyethersulfone solution with certain viscosity and containing cadmium ions and nickel ions;

preparing indium tin oxide conductive glass modified by cadmium ion and nickel ion polyether sulfone films: spin-coating the polyether sulfone solution containing the cadmium ions and the nickel ions on the surface of the cleaned indium tin oxide conductive glass at the spin-coating speed of 1000 r/min for 60 s to form a uniform polyether sulfone solution film containing the cadmium ions on the surface of the indium tin oxide conductive glass, and carrying out vacuum heat preservation on the obtained polyether sulfone solution film containing the cadmium ions at the temperature of 80 ℃ for 2 h to volatilize the solvent, so that the polyether sulfone film doped with the cadmium ions and the nickel ions is prepared on the surface of the indium tin oxide conductive glass;

preparing an electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode by laser induction: cooling the obtained polyether sulfone film modified indium tin oxide conductive glass doped with cadmium ions and nickel ions to room temperature, and adding CO₂Laser cutting carving machine working platform using CO₂The method comprises the steps of scanning the surfaces of the cadmium ion and nickel ion doped polyether sulfone films by laser, and directly converting the cadmium ion and nickel ion doped polyether sulfone films on the surfaces of indium tin oxide conductive glass into the electrocatalyst-semiconductor-three-dimensional porous graphene ternary composite photoelectrode in situ. The laser engraving parameters were as follows: the laser power is 4.0W, the laser engraving speed is 166 mm/s, the laser engraving resolution is 1200, and the laser defocusing distance is 0.3 cm.