Preparation method of polypyrrole-nickel doped cuprous oxide composite material
By growing nickel-doped cuprous oxide on a conductive substrate and polymerizing pyrrole monomers on its surface, polypyrrole-nickel-doped cuprous oxide composite material is prepared, which solves the problem of insufficient copper oxide photoelectric performance and improves the photoelectric conversion efficiency and the light response range have significantly improved its application potential in the field of optoelectronics.
Patent Information
- Application Number
- CN202411330843.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-24
- Publication Date
- 2024-12-17
AI Technical Summary
Copper oxide has problems with electron-hole recombination and photocorrosion in photoelectric applications, which limits its practical application, and existing methods are difficult to effectively improve its photoelectric performance.
Ni-doped cuprous oxide composite material was prepared by electrodeposition and hydrothermal method on the conductive substrate, and polypyrrole-nickel-doped cuprous oxide composite material was prepared by polymerizing pyrrole monomers on its surface using electropolymerization technology.
The photoelectric conversion efficiency of nickel-doped cuprous oxide is improved and the photoresponse range is widened, which significantly enhances its application value in the fields of photoelectro-catalyzed water decomposition, solar cells and photoelectrochemical sensing.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of composite nano material preparation, and more specifically to a method for preparing a polypyrrole-nickel doped cuprous oxide composite material by in-situ growth on a conductive substrate. Background Art
[0002] Cuprous oxide is a typical p-type semiconductor with a band gap of about 2.0 eV and is commonly used as a photocathode material. However, the problems of electron-hole recombination and photocorrosion greatly limit the practical application of cuprous oxide. At present, various methods have been developed to improve the photoelectric properties of cuprous oxide, such as morphology regulation, heterostructure construction, element doping, etc. Studies have shown that the introduction of heteroatoms into cuprous oxide can improve its band structure and performance. Nickel doping can cause slight lattice changes in cuprous oxide, thereby enhancing its photoelectric properties. Therefore, using nickel as a dopant to prepare nickel-doped cuprous oxide with excellent performance can greatly improve the photoelectric application performance of cuprous oxide.
[0003] Polypyrrole has a unique π-conjugated chain structure, showing high electrical conductivity, large carrier mobility and good processability. It has great application potential in the fields of photoelectrocatalysis, energy storage and electronic devices. In addition, polypyrrole has good near-infrared light absorption ability, which can effectively broaden the light response range of photoelectrodes. Based on the matching energy level structure of polypyrrole and nickel-doped cuprous oxide, polypyrrole is used to sensitize nickel-doped cuprous oxide to prepare polypyrrole-nickel-doped cuprous oxide composite materials, which can effectively promote its application in photoelectrocatalytic water splitting, solar cells and photoelectrochemical sensing. Summary of the invention
[0004] The purpose of the present invention is to firstly prepare nickel-doped cuprous oxide by growing it on a conductive substrate by combining an electrodeposition method and a hydrothermal method, and then polymerize pyrrole monomers on the surface of the nickel-doped cuprous oxide by means of an electropolymerization technology to obtain a polypyrrole-nickel-doped cuprous oxide composite material.
[0005] The preparation method of the polypyrrole-nickel doped cuprous oxide composite material specifically comprises the following steps: (1) Nickel-doped cuprous oxide was grown on the surface of fluorine-doped tin dioxide conductive glass (FTO). The process was divided into two steps. The first step was to grow copper nanoparticles on the FTO surface by electrodeposition. First, a 5 cm long and 1 cm wide FTO was placed in acetone, ethanol, and secondary water for ultrasonic cleaning for 15 minutes. Then, FTO was used as the working electrode, Ag / AgCl electrode was used as the reference electrode, and Pt electrode was used as the counter electrode. Copper nanoparticles were grown on the FTO surface by electrodeposition. The deposition electrolyte was a copper sulfate solution with a concentration of 0.2-0.5 M. The deposition voltage was 5-8 V and the deposition time was 20-40 seconds. After the deposition was completed, the FTO surface was washed with secondary water to obtain FTO coated with copper nanoparticles. The second step was to prepare nickel-doped cuprous oxide on the copper nanoparticle-coated FTO surface by hydrothermal method. First, 3-6 mL of 0.1-0.3 mM trisodium citrate, 7-10 mL of 10-13 mM copper chloride, and 1-3 mL of nickel chloride with a concentration of 10-13 mM and 20-25 mL of secondary water are mixed, and stirred at room temperature for 5 minutes to obtain a reaction mixture, and then 15 mL of the obtained reaction mixture is added to an autoclave with a volume of 25 mL, and the copper nanoparticle-coated FTO is placed in the autoclave with the conductive surface of the FTO facing downward, and finally the autoclave is placed in an oven and heated at 80-100 ° C for 6-10 hours. After the reaction is completed, it is naturally cooled to room temperature, and the copper nanoparticle-coated FTO surface is washed with secondary water and anhydrous ethanol in turn, and dried at 60 ° C for 1-3 hours to obtain nickel-doped cuprous oxide-coated FTO; (2) electropolymerizing and growing polypyrrole on the surface of the nickel-doped cuprous oxide-coated FTO obtained in step (1), using the nickel-doped cuprous oxide-coated FTO as a working electrode, an Ag / AgCl electrode as a reference electrode, and a Pt electrode as a counter electrode, growing polypyrrole on the surface of the nickel-doped cuprous oxide-coated FTO by means of electropolymerization technology, wherein the polymerization electrolyte is an acetonitrile solution containing pyrrole monomer and sodium perchlorate, wherein the concentration of the pyrrole monomer is 0.2-0.4 M, the concentration of the sodium perchlorate is 0.15-0.25 M, the polymerization time is 40-70 seconds, and the polymerization voltage is 0.7-1.0 V. After the polymerization is completed, the nickel-doped cuprous oxide-coated FTO surface is washed with anhydrous ethanol to obtain a polypyrrole-nickel-doped cuprous oxide composite material.
[0006] Beneficial effects of the present invention: (1) Nickel doping can induce the acceptor impurity energy level, narrow the band gap of cuprous oxide, and thus accelerate the separation and transfer of charges, effectively improving the photoelectric conversion efficiency of nickel-doped cuprous oxide.
[0007] (2) Polypyrrole has strong near-infrared light absorption ability, which can broaden the light response range of polypyrrole-nickel-doped cuprous oxide composites and greatly enhance their photoelectric properties.
[0008] (3) Polypyrrole-nickel-doped cuprous oxide composite materials not only have high charge separation efficiency but also exhibit strong light response ability. They have great application value in the fields of photoelectrocatalytic water splitting, solar cells and photoelectrochemical sensing. DETAILED DESCRIPTION
[0009] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.
[0010] Example 1 The preparation method of the polypyrrole-nickel doped cuprous oxide composite material is as follows: (1) Nickel-doped cuprous oxide was grown on the surface of fluorine-doped tin dioxide conductive glass (FTO). The process was divided into two steps. The first step was to grow copper nanoparticles on the FTO surface by electrodeposition. First, a 5 cm long and 1 cm wide FTO was placed in acetone, ethanol, and secondary water for ultrasonic cleaning for 15 minutes. Then, FTO was used as the working electrode, Ag / AgCl electrode was used as the reference electrode, and Pt electrode was used as the counter electrode. Copper nanoparticles were grown on the FTO surface by electrodeposition. The deposition electrolyte was a 0.4 M copper sulfate solution. The deposition voltage was 5 V and the deposition time was 30 seconds. After the deposition was completed, the FTO surface was washed with secondary water to obtain FTO coated with copper nanoparticles. The second step was to prepare nickel-doped cuprous oxide on the surface of FTO coated with copper nanoparticles by hydrothermal method. First, 5 mL of 0.3 mM trisodium citrate, 8 mL of 10 mM copper chloride, 2 mL of 10 mM nickel chloride, and 20 mL of secondary water was mixed and stirred at room temperature for 5 minutes to obtain a reaction mixture, and then 15 mL of the obtained reaction mixture was added to an autoclave with a volume of 25 mL, and the copper nanoparticle-coated FTO was placed in the autoclave with the conductive surface of the FTO facing downward. Finally, the autoclave was placed in an oven and heated at 80 ° C for 6 hours. After the reaction was completed, it was naturally cooled to room temperature, and the surface of the copper nanoparticle-coated FTO was washed with secondary water and anhydrous ethanol in turn, and dried at 60 ° C for 2 hours to obtain nickel-doped cuprous oxide-coated FTO; (2) The nickel-doped cuprous oxide-coated FTO surface obtained in step (1) is subjected to electropolymerization to grow polypyrrole, wherein the nickel-doped cuprous oxide-coated FTO is used as a working electrode, an Ag / AgCl electrode is used as a reference electrode, and a Pt electrode is used as a counter electrode. Polypyrrole is grown on the nickel-doped cuprous oxide-coated FTO surface by means of electropolymerization technology. The polymerization electrolyte is an acetonitrile solution containing pyrrole monomer and sodium perchlorate, wherein the concentration of the pyrrole monomer is 0.3 M, the concentration of the sodium perchlorate is 0.25 M, the polymerization time is 60 seconds, and the polymerization voltage is 0.8 V. After the polymerization is completed, the nickel-doped cuprous oxide-coated FTO surface is washed with anhydrous ethanol to obtain a polypyrrole-nickel-doped cuprous oxide composite material.
[0011] Example 2 The preparation steps are the same as those in Example 1, except that in step (1), the first step is to electro-deposit copper nanoparticles on the FTO surface, and the concentration of the copper sulfate solution used is 0.3 M.
[0012] Example 3 The preparation steps are the same as those in Example 1, except that in the second step of step (1), nickel-doped cuprous oxide is prepared on the surface of FTO coated with copper nanoparticles by a hydrothermal method, and the concentration of cupric chloride used is 12 mM.
[0013] Example 4 The preparation steps are the same as those in Example 1, except that in the second step of step (1), nickel-doped cuprous oxide is prepared on the surface of FTO coated with copper nanoparticles by means of a hydrothermal method, and the heating reaction time used is 10 hours.
[0014] Example 5 The preparation steps are the same as those in Example 1, except that the concentration of the pyrrole monomer used in step (2) is 0.4 M.
[0015] Example 6 The preparation steps are the same as those in Example 1, except that the polymerization time used in step (2) is 40 seconds.
Claims
1. A method for preparing a polypyrrole-nickel-doped cuprous oxide composite material, characterized in that The following steps are involved: (1) Nickel-doped cuprous oxide was grown on the surface of fluorine-doped tin dioxide conductive glass (FTO). The process was divided into two steps. The first step was to grow copper nanoparticles on the FTO surface by electrodeposition. First, a 5 cm long and 1 cm wide FTO was placed in acetone, ethanol, and secondary water for ultrasonic cleaning for 15 minutes. Then, FTO was used as the working electrode, Ag / AgCl electrode was used as the reference electrode, and Pt electrode was used as the counter electrode. Copper nanoparticles were grown on the FTO surface by electrodeposition. The deposition electrolyte was a copper sulfate solution with a concentration of 0.2-0.5 M. The deposition voltage was 5-8 V and the deposition time was 20-40 seconds. After the deposition was completed, the FTO surface was washed with secondary water to obtain FTO coated with copper nanoparticles. The second step was to prepare nickel-doped cuprous oxide on the copper nanoparticle-coated FTO surface by hydrothermal method. First, 3-6 mL of 0.1-0.3 mM trisodium citrate, 7-10 mL of 10-13 mM copper chloride, and 1-3 mL of nickel chloride with a concentration of 10-13 mM and 20-25 mL of secondary water are mixed, and stirred at room temperature for 5 minutes to obtain a reaction mixture, and then 15 mL of the obtained reaction mixture is added to an autoclave with a volume of 25 mL, and the copper nanoparticle-coated FTO is placed in the autoclave with the conductive surface of the FTO facing downward, and finally the autoclave is placed in an oven and heated at 80-100 ° C for 6-10 hours. After the reaction is completed, it is naturally cooled to room temperature, and the copper nanoparticle-coated FTO surface is washed with secondary water and anhydrous ethanol in turn, and dried at 60 ° C for 1-3 hours to obtain nickel-doped cuprous oxide-coated FTO; (2) electropolymerizing and growing polypyrrole on the surface of the nickel-doped cuprous oxide-coated FTO obtained in step (1), using the nickel-doped cuprous oxide-coated FTO as a working electrode, an Ag / AgCl electrode as a reference electrode, and a Pt electrode as a counter electrode, growing polypyrrole on the surface of the nickel-doped cuprous oxide-coated FTO by means of electropolymerization technology, wherein the polymerization electrolyte is an acetonitrile solution containing pyrrole monomer and sodium perchlorate, wherein the concentration of the pyrrole monomer is 0.2-0.4 M, the concentration of the sodium perchlorate is 0.15-0.25 M, the polymerization time is 40-70 seconds, and the polymerization voltage is 0.7-1.0 V. After the polymerization is completed, the nickel-doped cuprous oxide-coated FTO surface is washed with anhydrous ethanol to obtain a polypyrrole-nickel-doped cuprous oxide composite material.