阅读说明：本技术 铂-羟基氧化镍-氧化亚铜-金复合纳米纸的制备方法 (Preparation method of platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper ) 是由 杨红梅 于京华 张彦 李正林 葛慎光 于 2020-07-23 设计创作，主要内容包括：本发明公开了一种铂-羟基氧化镍-氧化亚铜-金复合纳米纸的制备方法,首先利用双侧生长法在纸基底表面生长铂纳米粒子层,获得导电性能良好的铂纸基底,然后利用电沉积法在铂纸基底表面依次沉积羟基氧化镍、氧化亚铜纳米颗粒和金纳米粒子层,获得铂-羟基氧化镍-氧化亚铜-金复合纳米纸。羟基氧化镍和金纳米粒子作为助催化剂可以有效地加速氧化亚铜光生电子和空穴的分离,阻止氧化亚铜自腐蚀,极大地提高氧化亚铜的应用稳定性。该纳米纸制备方法简单、高效,有利于大批量生产,对光电化学分解水、光电催化等领域具有重要的意义。(The invention discloses a preparation method of platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper. The nickel oxyhydroxide and the gold nanoparticles are used as the cocatalyst, so that the separation of the photo-generated electrons and holes of the cuprous oxide can be effectively accelerated, the cuprous oxide is prevented from self-corrosion, and the application stability of the cuprous oxide is greatly improved. The preparation method of the nano paper is simple and efficient, is beneficial to mass production, and has important significance in the fields of photoelectrochemistry water decomposition, photoelectrocatalysis and the like.)

1. A preparation method of platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper is characterized by comprising the following steps:

(1) preparing a platinum paper substrate, wherein the process is divided into 2 steps, the first step is to design a paper substrate wax printing pattern by using computer software Adobe illustrator CS4, print the designed wax printing pattern on chromatographic paper by using a wax printer with the model of Color Qube 8580, and finally heat the chromatographic paper printed by the wax for 30 s in an oven at 150 ℃ to obtain a hydrophilic functional area and a hydrophobic wax dyeing area; secondly, growing a platinum nanoparticle layer on the obtained hydrophilic functional area by using a bilateral growth method, firstly, dripping 80-120 mu L of newly prepared mixed liquid consisting of chloroplatinic acid with the concentration of 200-250 mM and sodium borohydride with the concentration of 20-25 mM onto the front side of the hydrophilic functional area, carrying out ice bath treatment on the sodium borohydride solution in advance for 30 min, then standing and reacting at room temperature for 10-20 min to complete the growth process of the platinum nanoparticles, and finally, repeating the growth process of the platinum nanoparticles on the back side of the hydrophilic functional area to obtain a platinum paper substrate;

(2) preparing platinum-nickel oxyhydroxide-cuprous oxide-gold composite nanopaper, which is divided into 3 steps, wherein in the first step, the platinum paper substrate obtained in the step (1) is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, nickel oxyhydroxide is electrodeposited on the surface of the platinum paper substrate by using a three-electrode system, a deposited electrolyte is a nickel nitrate solution with the concentration of 0.1-0.3M, the pH of the electrolyte is adjusted to 5-7 by sodium hydroxide with the concentration of 0.1M, before deposition of the electrolyte, argon is used for deoxidizing for 30-60 min, the deposition voltage is 1.0-1.5V, the deposition time is 10-20 min, and the intensity of the whole deposition process is 100mW/cm²After deposition is finished, washing the surface of the platinum paper substrate by secondary water and naturally drying at room temperature to obtain platinum-nickel oxyhydroxide composite nano paper; the second step is to electrodeposit cuprous oxide nano particles on the surface of the platinum-nickel oxyhydroxide composite nano paper by utilizing a three-electrode system consisting of platinum-nickel oxyhydroxide composite nano paper, an Ag/AgCl reference electrode and a Pt counter electrode, wherein the deposition electrolyte is a mixed solution consisting of lactic acid with the concentration of 2-4M and copper sulfate with the concentration of 0.1-0.3M, the pH of the deposition electrolyte is adjusted to 9-11 by sodium hydroxide with the concentration of 0.1M, the deposition temperature is 30-50 ℃, the deposition voltage is-0.2 to-0.4V, the deposition time is 15-25 min, after the deposition is finished, the surface of the platinum-nickel oxyhydroxide composite nano paper is sequentially washed by secondary water and ethanol, drying at 60 deg.C for 30 min to obtain platinum-nickel oxyhydroxide-cuprous oxide composite nanopaper; the third step is to use the platinum-hydroxyl nickel oxide-cuprous oxide composite nano paper as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt electrode as a counter electrode, and to electrodeposit a gold nano particle layer on the surface of the platinum-hydroxyl nickel oxide-cuprous oxide composite nano paper and depositAnd the electrolyte is a chloroauric acid solution with the concentration of 20-30 mM, the deposition voltage is minus 0.2 to minus 0.3V, the deposition time is 60-120 s, after the deposition is finished, the surface of the platinum-nickel oxyhydroxide-cuprous oxide composite nano paper is washed by secondary water and naturally dried at room temperature, and the platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper is obtained.

Technical Field

The invention relates to the technical field of composite nano material preparation technology and paper chip functional treatment, in particular to a preparation method of platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper.

Background

Cuprous oxide is used as a P-type semiconductor with narrow band gap (2.1-2.3 eV), has the advantages of no toxicity, rich sources, low cost and the like, and is a good photocathode material. Based on the excellent characteristics of cuprous oxide, the cuprous oxide can be widely applied to the fields of photoelectrochemical water decomposition, lithium ion batteries, photoelectrocatalysis and the like. However, the self-corrosiveness of cuprous oxide seriously affects the stability and reduces the application performance of cuprous oxide. Therefore, it is necessary to introduce a cocatalyst to prepare a cuprous oxide-based composite material, improve the separation efficiency of the photogenerated electrons and holes, and enhance the practical application performance of the material.

The paper is composed of criss-cross fibers, and the unique three-dimensional network structure of the paper enables the paper to have a large surface area, so that a large number of active sites can be provided for functionalizing different nano materials. The unique construction of paper itself makes it widely used as a low cost electrode substrate material. The method combines the excellent characteristics of the paper substrate and the composite nano material to prepare the platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper with excellent performance, and has important significance in the fields of photoelectrochemical water decomposition, lithium ion batteries, photoelectrocatalysis and the like.

Disclosure of Invention

The invention aims to grow a layer of platinum nano particles on the surface of paper fibers by using a bilateral growth method to obtain a platinum paper substrate with good conductivity, and then sequentially deposit nickel oxyhydroxide, cuprous oxide and gold nano particles on the surface of the platinum paper substrate to prepare the platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper.

The preparation method of the platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper specifically comprises the following steps:

(1) preparing a platinum paper substrate, wherein the process is divided into 2 steps, the first step is to design a paper substrate wax printing pattern by using computer software Adobe illustrator CS4, print the designed wax printing pattern on chromatographic paper by using a wax printer with the model of Color Qube 8580, and finally heat the chromatographic paper printed by the wax for 30 s in an oven at 150 ℃ to obtain a hydrophilic functional area and a hydrophobic wax dyeing area; secondly, growing a platinum nanoparticle layer on the obtained hydrophilic functional area by using a bilateral growth method, firstly, dripping 80-120 mu L of newly prepared mixed liquid consisting of chloroplatinic acid with the concentration of 200-250 mM and sodium borohydride with the concentration of 20-25 mM onto the front side of the hydrophilic functional area, carrying out ice bath treatment on the sodium borohydride solution in advance for 30 min, then standing and reacting at room temperature for 10-20 min to complete the growth process of the platinum nanoparticles, and finally, repeating the growth process of the platinum nanoparticles on the back side of the hydrophilic functional area to obtain a platinum paper substrate;

(2) preparing platinum-nickel oxyhydroxide-cuprous oxide-gold composite nanopaper, which is divided into 3 steps, wherein in the first step, the platinum paper substrate obtained in the step (1) is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, nickel oxyhydroxide is electrodeposited on the surface of the platinum paper substrate by using a three-electrode system, a deposited electrolyte is a nickel nitrate solution with the concentration of 0.1-0.3M, the pH of the electrolyte is adjusted to 5-7 by sodium hydroxide with the concentration of 0.1M, before deposition of the electrolyte, argon is used for deoxidizing for 30-60 min, the deposition voltage is 1.0-1.5V, the deposition time is 10-20 min, and the intensity of the whole deposition process is 100mW/cm²After deposition is finished, washing the surface of the platinum paper substrate by secondary water and naturally drying at room temperature to obtain platinum-nickel oxyhydroxide composite nano paper; the second step is to electrodeposit cuprous oxide nano particles on the surface of the platinum-nickel oxyhydroxide composite nano paper by utilizing a three-electrode system consisting of platinum-nickel oxyhydroxide composite nano paper, an Ag/AgCl reference electrode and a Pt counter electrode, wherein the deposition electrolyte is a mixed solution consisting of lactic acid with the concentration of 2-4M and copper sulfate with the concentration of 0.1-0.3M, the pH of the deposition electrolyte is adjusted to 9-11 by sodium hydroxide with the concentration of 0.1M, the deposition temperature is 30-50 ℃, the deposition voltage is-0.2 to-0.4V, the deposition time is 15-25 min, after the deposition is finished, the surface of the platinum-nickel oxyhydroxide composite nano paper is sequentially washed by secondary water and ethanol, drying at 60 deg.C for 30 min to obtain platinum-nickel oxyhydroxide-cuprous oxide composite nanopaper; the third step is to electrodeposit on the surface of the platinum-hydroxyl nickel oxide-cuprous oxide composite nano paper by using the platinum-hydroxyl nickel oxide-cuprous oxide composite nano paper as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt electrode as a counter electrodeAnd (3) a gold nanoparticle layer, wherein the deposition electrolyte is a chloroauric acid solution with the concentration of 20-30 mM, the deposition voltage is-0.2 to-0.3V, the deposition time is 60-120 s, after the deposition is finished, the surface of the platinum-nickel oxyhydroxide-cuprous oxide composite nanopaper is washed by secondary water and naturally dried at room temperature, and the platinum-nickel oxyhydroxide-cuprous oxide-gold composite nanopaper is obtained.

The invention has the beneficial effects that:

(1) the prepared platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper has a large surface area, can provide a large number of effective active sites, and is favorable for greatly improving the photoelectric catalytic performance.

(2) The hydroxyl nickel oxide and the gold are used as the promoters, so that the separation of photoproduction electrons and holes can be effectively accelerated, the self-corrosion of cuprous oxide is prevented, and the application stability of the cuprous oxide is greatly improved.

(3) The platinum-nickel oxyhydroxide-cuprous oxide-gold composite nano paper is simple in preparation method and low in cost, can be produced in large scale, and has high application value in the fields of photoelectrochemical water decomposition, lithium ion batteries, photoelectrocatalysis and the like.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.