CN110344111B

CN110344111B - Synthesis method and application of copper-gallium-indium ternary polycrystalline material

Info

Publication number: CN110344111B
Application number: CN201910589409.4A
Authority: CN
Inventors: 崔小强; 马星程
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2019-07-02
Filing date: 2019-07-02
Publication date: 2020-12-29
Anticipated expiration: 2039-07-02
Also published as: CN110344111A

Abstract

The invention discloses a preparation method of a copper-gallium-indium ternary polycrystalline material and the copper-gallium-indium ternary polycrystalline material is used as an electrocatalytic carbon dioxide reduction catalyst. The invention mainly utilizes the easy alloying interaction of binary gallium indium liquid metal and a copper substrate in alkali liquor, and firstly forms copper gallium alloy and precipitated simple substance indium in situ on the copper substrate by ultrasonic. And then, further etching the alloy by using strong alkali liquor to remove part of element gallium, and successfully obtaining the ternary copper-gallium-indium polycrystalline material with pores on the surface. And applied to the test of the electrocatalytic carbon dioxide reduction property. The invention successfully constructs the polycrystalline ternary copper gallium indium/copper heterostructure material on the foamy copper self-supporting electrode substrate in situ, realizes the regulation and control of the porous structure and the element proportion through alloy templating and dealloying etching, and improves the catalytic activity of electrocatalysis carbon dioxide reduction.

Description

Synthesis method and application of copper-gallium-indium ternary polycrystalline material

Technical Field

The invention belongs to the field of clean and sustainable novel energy preparation and application, and particularly relates to preparation of a copper-gallium-indium ternary polycrystalline material and application of the copper-gallium-indium ternary polycrystalline material in electrocatalysis carbon dioxide reduction.

Background

In recent years, the greenhouse effect due to excessive emission of carbon dioxide has caused serious environmental problems. The conversion of excess carbon dioxide into usable carbonaceous energy and the mitigation of the negative effects of the greenhouse effect have been the focus of attention in recent years, and the development of new carbon dioxide reduction catalysts is urgent. A large number of catalysts have been discovered, with copper-based catalysts being the most widely studied. However, pure copper materials on the market without modification are not satisfactory in the field of carbon dioxide reduction, and show very low catalytic efficiency of carbon dioxide reduction. The method for modifying the self-supporting copper electrode into the good carbon dioxide reduction catalyst by a simple and efficient method has practical value and always attracts the exploration of extensive researchers.

Gallium-indium binary liquid metal as a non-toxic and environment-friendly novel metal material has shown great prospects in the aspects of catalysis, sensing, two-dimensional material synthesis, stress regulation, surface wetting and the like, and the constituent elements of the gallium-indium binary liquid metal have the potential of catalyzing carbon dioxide reduction. However, the gallium indium binary liquid metal itself shows electrocatalytic carbon dioxide reduction inertness, which greatly limits the expansion of the related applications. At present, liquid metal is directly applied to carbon dioxide reduction as an electrode carrier, but the liquid metal does not participate in reduction reaction per se. The alloying interaction between the liquid metal and the copper substrate is utilized to modify the two to form a new material suitable for electrocatalytic carbon dioxide reduction, and the application is also rarely reported.

Disclosure of Invention

The invention aims to provide a synthetic method of a copper-gallium-indium ternary polycrystalline material and application thereof based on a simple and rapid ultrasonic and etching method aiming at the defects of the prior art and the defects of properties. The synthesized material, especially the copper gallium indium ternary polycrystalline material synthesized by taking the copper foam as the base material, shows good capability of carbon dioxide electrocatalytic reduction to carbon monoxide, can be directly used as an electrode compared with commercial copper substrates and liquid metal, and greatly improves the catalytic performance.

The purpose of the invention is realized by the following technical scheme: a method for synthesizing ternary copper gallium indium polycrystalline material comprises the following steps:

(1) and immersing the copper sheet in the binary gallium indium liquid metal, stirring for 20-120 min, and taking out to obtain the copper sheet with the uniform binary gallium indium liquid metal adhered on the surface.

(2) Immersing the copper sheet with the uniform binary gallium indium liquid metal adhered on the surface, obtained in the step (1), in a 0.05-1M potassium hydroxide solution for ultrasonic treatment for 3-10 min, taking out the copper sheet after the solution is turbid, and washing the copper sheet with deionized water to obtain a silver gray copper sheet.

(3) And (3) standing and drying the copper sheet in the step (2) in air for 4-6 h, immersing the copper sheet in 2-3M potassium hydroxide solution again, standing, taking out the copper sheet after 30min, washing with deionized water, and naturally drying to obtain the ternary copper gallium indium polycrystalline material.

Preferably, the copper sheet is a foam copper sheet.

Further, the clean foam copper sheet in the step (1) is obtained by the following steps: the clean foam copper sheet in the step (1) is obtained through the following steps: immersing the foamed copper with the specification of 10mm 15mm 2mm in acetone, 0.5M dilute hydrochloric acid and ethanol in sequence, performing ultrasonic treatment for 15min, and drying the foamed copper sheet subjected to ultrasonic treatment by using inert gas.

The invention also relates to a ternary copper gallium indium polycrystalline material synthesized by the method, in particular to application of the ternary copper gallium indium polycrystalline material synthesized by taking copper foam as a base material in electrocatalysis carbon dioxide reduction.

The invention has the beneficial effects that: the copper-gallium-indium ternary polycrystalline composite material with pores on the surface is obtained by a simple ultrasonic and etching method, can be directly used as a self-supporting electrode to be applied to the test of electrocatalytic carbon dioxide reduction, greatly improves the intrinsic catalytic activity due to templating and element proportion adjustment, and increases the yield of carbon monoxide generation and Faraday efficiency.

Drawings

FIG. 1 is an optical photograph of ternary polycrystalline composite material of copper, gallium and indium prepared by the present invention. a) B), c) and d) respectively correspond to original foam copper, foam copper stirred in liquid metal, a material obtained after ultrasonic treatment in 0.05M KOH after stirring, and a copper gallium indium ternary polycrystalline composite material finally formed after the material obtained after ultrasonic treatment is soaked in 3M KOH.

FIG. 2 is a Scanning Electron Microscope (SEM) picture of the ternary polycrystalline composite material of copper, gallium and indium prepared by the present invention. a) And b) SEM at different sizes.

Figure 3 is an X-ray diffraction (XRD) characterization of the sequence of figure one corresponding to the four materials.

FIG. 4 is an electrocatalytic carbon dioxide reduction property test for the four materials in sequence in FIG. one, where a) is the carbon monoxide partial current density and b) is the carbon monoxide Faraday efficiency.

Detailed Description

The invention provides a method for synthesizing a ternary copper gallium indium polycrystalline material, which can form a blocky composite material on the surface of a substrate in a template mode through the alloying interaction of gallium indium in liquid metal and a copper substrate, and then realize the selective etching of gallium by concentrated alkali by utilizing the activity sequence of the reaction of the metal and the concentrated alkali, thereby constructing the porous copper gallium indium ternary polycrystalline material with adjustable element proportion. The generation of the porous structure and the etching of the inert Ga element respectively promote the adsorption of carbon dioxide gas and expose more active sites, thereby synergistically enhancing the electroreduction catalytic capability of carbon dioxide.

The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.

Example 1:

the preparation method of the copper-gallium-indium ternary polycrystalline composite material specifically comprises the following steps:

(1) firstly, respectively using acetone, 0.5M dilute hydrochloric acid and ethanol to perform ultrasonic treatment on 10mm by 15mm by 2mm foam copper for 15min, drying the cleanly treated foam copper sheet by inert gas, quickly placing the cleanly treated foam copper sheet in 2mL of binary gallium indium liquid metal, slightly stirring for 20min, and taking out the foam copper after absorbing the relatively uniform binary gallium indium liquid metal with metal luster on the surface to obtain the foam copper with the liquid metal adhered on the surface.

(2) And (2) placing the foamy copper sheet obtained in the step (1) in 2mL of 0.05M potassium hydroxide solution for ultrasonic treatment for 3min, taking out the foamy copper sheet after the solution is turbid, and washing with deionized water to obtain silver gray foamy copper.

(3) And (3) standing and drying the copper foam in the step (2) in the air for 4h, then placing the dried copper foam in 4mL of 3M potassium hydroxide solution again for standing, observing the generation of bubbles, taking out the copper foam after 30min, washing the copper foam with deionized water, and naturally drying the copper foam at room temperature to obtain the final material.

FIG. 1 is an optical photograph of the change in material before and after the preparation of the present invention. It can be seen that the final prepared material is very different from the initial copper foam, but the base structure of the copper foam is still remained, and the copper foam can be directly used as an electrode for subsequent processing.

FIG. 2 is a Scanning Electron Microscope (SEM) picture of the ternary polycrystalline composite material of copper, gallium and indium prepared by the present invention. a) And b) SEM at different sizes. Through SEM, it can be seen that the ternary polycrystalline composite material of copper, gallium and indium uniformly grows on the substrate of the foamed copper, and the block-shaped square blocks also have very obvious hole structures, which is beneficial to promoting the adsorption of carbon dioxide gas.

FIG. 3 is an X-ray diffraction analysis (XRD) of the ternary polycrystalline composite material of copper, gallium and indium prepared by the present invention, and compared with the material obtained in the previous step, the obvious finding is that the liquid metal reacts with the foamed copper substrate in alkali to form CuGa₂Alloying and solidifying the indium in the liquid metal separately,and under the final etching of alkali liquor, the content of gallium is reduced, and the rationality of the whole preparation process is proved.

FIG. 4 shows the property test of the electrocatalytic reduction of carbon dioxide of the ternary polycrystalline copper-gallium-indium composite material prepared by the present invention, and compared with the material obtained in the previous step, the final synthesized polycrystalline copper-gallium-indium composite material has greatly improved current density and Faraday efficiency, and the Faraday efficiency of carbon monoxide reaches more than 70%. The improvement in performance can be attributed to the templating and element ratio modulating effects.

Example 2:

(1) firstly, respectively using acetone, 0.5M dilute hydrochloric acid and ethanol to perform ultrasonic treatment on 10mm by 15mm by 2mm foam copper for 15min, drying the cleanly treated foam copper sheet by inert gas, quickly placing the cleanly treated foam copper sheet in 2mL of binary gallium indium liquid metal, slightly stirring for 120min, and taking out the foam copper after absorbing the relatively uniform binary gallium indium liquid metal with metal luster on the surface to obtain the foam copper with the liquid metal adhered on the surface.

(2) And (3) placing the foamy copper sheet obtained in the step (1) in 2mL of 1M potassium hydroxide solution for ultrasonic treatment for 10min, taking out the foamy copper sheet after the solution is turbid, and washing the foamy copper sheet with deionized water to obtain silver gray foamy copper.

(3) And (3) standing and drying the copper foam in the step (2) in the air for 6h, then placing the dried copper foam in 4mL of 2M potassium hydroxide solution again for standing, observing the generation of bubbles, taking out the copper foam after 30min, washing the copper foam with deionized water, and naturally drying the copper foam at room temperature to obtain the final material.

The copper-gallium-indium ternary material prepared by the embodiment still keeps the substrate structure of the foam copper, can be directly used as an electrode, and is convenient for subsequent processing. And the ternary copper-gallium-indium polycrystalline composite material uniformly grows on the substrate of the foam copper, and the blocky square blocks also have very obvious hole structures, so that the adsorption of carbon dioxide gas is promoted.

The final synthesized copper-gallium-indium polycrystalline composite material is greatly improved in current density and Faraday efficiency, and the Faraday efficiency of carbon monoxide reaches 71.4% in-0.7 Vvs. The improvement in performance can be attributed to the templating and element ratio modulating effects.

The preparation method of the copper-gallium-indium ternary polycrystalline composite material prepared by the method is simple, high in repeatability and strong in operability. The obtained material is used as a self-supporting electrode, and shows good catalytic performance in electrocatalytic carbon dioxide reduction.

Claims

1. A synthetic method of ternary copper gallium indium polycrystalline material is characterized by comprising the following steps:

(1) immersing the foamy copper in acetone, 0.5M dilute hydrochloric acid and ethanol in sequence, performing ultrasonic treatment for 15min, and drying the foamed copper sheet subjected to ultrasonic treatment by inert gas;

(2) immersing the foamed copper sheet treated in the step (1) in the binary gallium indium liquid metal, stirring for 20-120 min, and taking out to obtain a copper sheet with uniform binary gallium indium liquid metal adhered to the surface;

(3) immersing the copper sheet with the uniform binary gallium indium liquid metal adhered on the surface, obtained in the step (2), in a 0.05-1M potassium hydroxide solution for ultrasonic treatment for 3-10 min, taking out the copper sheet after the solution is turbid, and washing the copper sheet with deionized water to obtain a silver gray copper sheet;

(4) and (4) standing and drying the copper sheet in the step (3) in air for 4-6 h, immersing the copper sheet in 2-3M potassium hydroxide solution again, standing, taking out the copper sheet after 30min, washing with deionized water, and naturally drying to obtain the ternary copper gallium indium polycrystalline material.

2. The application of the ternary copper-gallium-indium polycrystalline material synthesized by the method in claim 1 in electrocatalytic carbon dioxide reduction.