CN110938844B - Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof - Google Patents

Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof Download PDF

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CN110938844B
CN110938844B CN201911108785.3A CN201911108785A CN110938844B CN 110938844 B CN110938844 B CN 110938844B CN 201911108785 A CN201911108785 A CN 201911108785A CN 110938844 B CN110938844 B CN 110938844B
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copper
dimensional
tin
foam
preparation
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CN110938844A (en
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康雄武
王继刚
陈少伟
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Abstract

The invention discloses a self-supporting three-dimensional copper-tin alloy material and a preparation method and application thereof. The preparation method comprises the following steps: (1) firstly, cleaning the foam copper to remove surface pollutants; dissolving potassium hydroxide and tin dichloride in deionized water to serve as electrolyte, taking the cleaned copper foam as a working electrode, carrying out constant-current electrolysis in a three-electrode system, washing the working electrode after the electrolysis is finished, and carrying out vacuum drying to obtain a three-dimensional foam tin-based precursor; (2) and placing the three-dimensional foam tin-based precursor in an inert atmosphere, and heating to react so as to obtain the self-supporting three-dimensional copper-tin alloy material. Compared with other noble metal catalysts, the invention can directly synthesize the copper-tin alloy on the three-dimensional foam under a mild condition, has little pollution to the environment, does not need expensive equipment and complex preparation procedures, and achieves the aim of reducing the preparation cost.

Description

Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemical reduction of carbon dioxide, and particularly relates to a self-supporting three-dimensional copper-tin alloy material and a preparation method and application thereof.
Background
With the rapid development of the industry, fossil fuels are used as main energy more and more rapidly, but the energy is limited and exhausted, and the ecological environment of the earth is seriously damaged, wherein the most important factor is the "greenhouse effect", and the most important reason for the "greenhouse effect" is the gradual increase of the emission of carbon dioxide. Therefore, reducing the production of carbon dioxide or converting carbon dioxide into useful materials is crucial for environmental protection. In the treatment of CO in a plurality of ways2In the method of (1), electrochemical reduction of CO2Has gained wide attention because of electrochemical reduction of CO2The method has the following advantages: the method has the advantages of relatively simple and convenient operation conditions (such as the operation can be carried out at normal temperature and normal pressure), easy control of the process (controlled by electrode potential and reaction temperature), utilization of clean and renewable energy sources (such as solar energy and wind energy), compactness, flexibility, modularization, easy amplification production and the like of an electrochemical reaction system. But CO2The chemical property is relatively stable, the reaction activity is low, and therefore, the preparation of high-efficiency catalysts is needed.
For electrocatalytic reduction of CO2The electrode materials of (1) are many, and some catalysts using noble metals Au and Ag have excellent catalytic performance, but the current density is low, and meanwhile, the commercial application of the catalysts is seriously hindered due to the high cost and scarcity of the noble metals.
Materials with three-dimensional structures have been developed to increase the surface area, expose more active sites, and increase the current density during the reaction. Because the metal Cu has rich resources and priceLow cost, simple synthesis method and the like, and the Cu metal can directly react with CO under higher current efficiency2Catalytic activity can be stabilized for a while by reduction to hydrocarbons, and thus it is widely used in research of electrode materials, but metallic Cu has an ultra-high overpotential, hindering practical applications. The activity of the catalyst has a great relationship with the surface structure and the active surface area of the catalyst, and the surface structure of the catalyst is changed by loading some metals with higher hydrogen evolution potential on the surface through a chemical method, so that the activity of the catalyst is changed. Therefore, it is a great challenge to synthesize a catalyst with good overall performance and low cost.
“Electrochemical reduction of CO2to format catalyzed by electroplated on copper foam "discloses deposition of Sn on foamed Cu and subsequent reduction of CO2, but they have lower faradaic efficiency, lower current density and greater overpotential for formic acid production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a self-supporting three-dimensional copper-tin alloy material and a preparation method and application thereof. The invention utilizes the catalytic action of preparing copper-tin alloy (CuSn) on three-dimensional foam to efficiently reduce CO2And (3) preparing formic acid.
The object of the present invention is achieved by at least one of the following technical means.
A preparation method of a self-supporting three-dimensional copper-tin alloy material comprises the following steps:
(1) preparation of three-dimensional foam copper-tin precursor
Firstly, cleaning the foam copper to remove surface pollutants; dissolving potassium hydroxide and tin dichloride in deionized water to serve as electrolyte, taking the cleaned copper foam as a working electrode, carrying out constant-current electrolysis in a three-electrode system, washing the working electrode after the electrolysis is finished, and carrying out vacuum drying to obtain a three-dimensional foam tin-based precursor;
(2) preparation of self-supporting three-dimensional copper-tin alloy material
And placing the three-dimensional foam tin-based precursor in an inert atmosphere, and heating to react so as to obtain the self-supporting three-dimensional copper-tin alloy material.
Further, in the step (1), the step of cleaning the copper foam is to perform ultrasonic treatment on the copper foam in diluted hydrochloric acid, ethanol and deionized water respectively.
Further, in the step (1), the concentration of tin dichloride in the electrolyte is 0.01-0.1mol/L, and the concentration of sodium hydroxide is 1-3 mol/L.
Further, in the step (1), an Ag/AgCl electrode or a calomel electrode is used as a reference electrode during electrolysis, and a Pt wire or a carbon rod is used as a counter electrode.
Further, in the step (1), the temperature of vacuum drying is 50-70 ℃ and the time is 6-24 h.
Further, in the step (1), the electrolysis time is 1000-.
Further, in the step (2), the reaction temperature is 200-.
The self-supporting three-dimensional copper-tin alloy material prepared by the preparation method.
The self-supporting three-dimensional copper-tin alloy material is used for reducing CO in electrochemistry2The use of (1).
Compared with the prior art, the invention utilizes the porous structure of the three-dimensional foam, the copper-tin alloy is directly grown on the foam, larger specific surface area can be provided, the copper-tin alloy is formed into an alloy through calcination, and the alloy can possibly show specific properties compared with single metal in the catalysis process, such as synergistic effect, so that the improvement of the catalytic performance is promoted. The three-dimensional foam copper-tin alloy electrodes with different alloy contents can be realized by adjusting parameters such as the time of electrodeposition and the like in the synthesis process. Compared with other noble metal catalysts, the invention can directly synthesize the copper-tin alloy on the three-dimensional foam under mild conditions, has little pollution to the environment, does not need expensive equipment and complex preparation procedures, and achieves the aim of reducing the preparation cost.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of copper foam of examples 1-3 after deposition of metallic tin thereon;
FIG. 2 is an X-ray diffraction (XRD) pattern of the copper foam, tin deposited on the copper foam, and calcination of examples 1-3;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the copper foam deposit of examples 1-3 after the metal tin has been calcined;
FIG. 4 is a Transmission Electron Microscope (TEM) image at different magnifications of the copper foam deposit metallic tin of example 2 after calcination;
FIG. 5 is an X-ray electron spectroscopy (XPS) graph of the copper foam deposit of examples 1-3 after calcination of metallic tin;
FIG. 6 is the CO content of the copper foam deposited metallic tin of examples 1-3 after calcination2Performance of the reduction is plotted.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The method comprises the following steps of cleaning the copper foam, and then carrying out electrolytic reaction on the copper foam serving as a working electrode, wherein the cleaning is to carry out ultrasonic treatment on the copper foam (1cm multiplied by 1cm) in dilute hydrochloric acid (2M), ethanol and deionized water respectively so as to remove oxides and organic pollutants on the surface.
Example 1
Dissolving 11.2g of potassium hydroxide (2M) and 1.12g of tin dichloride (0.05M) by using 100 mL of deionized water, transferring the solution into an electrolytic cell, then, taking the treated copper foam as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt wire as a counter electrode, washing the solution for several times by using deionized water and ethanol after carrying out constant current electrolysis for 1000s in a three-electrode system, and then drying the solution overnight in a vacuum oven with the temperature of 60 ℃ to obtain a three-dimensional foam tin-based precursor (marked as CuSn 5). And heating the three-dimensional foam tin-based precursor to 300 ℃ in an Ar atmosphere in a tubular furnace, reacting and preserving heat for 3h to obtain the three-dimensional foam load copper-tin alloy electrode material (marked as CuSn-5C).
Example 2
Dissolving 11.2g of potassium hydroxide (2M) and 1.12g of tin dichloride (0.05M) by using 100 mL of deionized water, transferring the solution into an electrolytic cell, then, taking the treated copper foam as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt wire as a counter electrode, washing the solution for several times by using deionized water and ethanol after constant current electrolysis is carried out for 2000s in a three-electrode system, and then drying the solution overnight in a vacuum oven with the temperature of 60 ℃ to obtain a three-dimensional foam tin-based precursor (marked as CuSn 10). And heating the three-dimensional foam tin-based precursor to 300 ℃ in an Ar atmosphere in a tubular furnace, reacting and preserving heat for 3h to obtain the three-dimensional foam load copper-tin alloy electrode material (marked as CuSn-10C).
Example 3
Dissolving 11.2g of potassium hydroxide (2M) and 1.12g of tin dichloride (0.05M) by using 100 mL of deionized water, transferring the solution into an electrolytic bath, then, taking the treated copper foam as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt wire as a counter electrode, washing the solution for several times by using deionized water and ethanol after carrying out constant current electrolysis for 3000s in a three-electrode system, and then drying the solution overnight in a vacuum oven with the temperature of 60 ℃ to obtain a three-dimensional foam tin-based precursor (marked as CuSn 15). And heating the three-dimensional foam tin-based precursor to 300 ℃ in an Ar atmosphere in a tubular furnace, reacting and preserving heat for 3h to obtain the three-dimensional foam load copper-tin alloy electrode material (marked as CuSn-15C).
Referring to fig. 1 a-c, corresponding SEM images of the three-dimensional foam tin-based precursor of examples 1-3, it can be clearly seen that the copper foam skeleton is covered with a layer of spherical small particles, and the surface coverage is tighter as the deposition amount increases.
Referring to figures 2 a-c, corresponding XRD patterns after copper foam, copper foam deposition and calcination of examples 1-3, it can be seen that after tin deposition, four additional diffraction peaks are seen at 30.6 °, 32.0 °, 44.9 ° and 62.5 °, corresponding to (200), (101), (211) and (112) planes of Sn, respectively, in addition to the three major peaks of copper foam identified at 43.3 °, 50.4 ° and 74.1 °. After calcination, the diffraction peak of metal Sn disappears, and new diffraction peaks appear and correspond to Cu at 30.1 DEG respectively6Sn5(PDF 45-1488) and (22-1) planes at 37.7 DEG, 41.7 DEG, 57.5 DEG correspond to Cu3(01) of Sn (PDF 01-1240)60) Crystal planes of (002) and (0162). Indicating that the alloy was formed after the calcination treatment.
Referring to a-c in fig. 3, corresponding to SEM images of tin deposited on the copper foam of examples 1-3 after calcination, it can be clearly observed that the original spherical Sn nanoparticles on the surface form irregular morphology on the surface of the copper foam after calcination.
Referring to a and b in fig. 4, corresponding to TEM images with different magnifications of Sn deposited by the copper foam of example 2 after calcination, it can be seen from a in fig. 4 that the morphology after calcination is changed into irregular prism-like morphology, which is consistent with the morphology observed by SEM. And it is observed from b in FIG. 4 that the lattice fringe spacing is 0.296nm and 0.208nm, respectively, which correspond to Cu, respectively6Sn5(22-1) plane of (C) and Cu3Sn (2120) crystal plane.
Referring to fig. 5, XPS graphs of Sn deposited by the copper foam of corresponding examples 1 to 3 and then calcined, it can be seen that the prepared material only contains metallic Cu and Sn, and no other impurities are doped, confirming the higher purity of the material.
Referring to FIG. 6, a graph comparing the performance of Sn deposited by copper foam deposition according to examples 1 to 3 after calcination is tested under normal temperature and pressure conditions in a saturated CO atmosphere2The electrolysis is carried out by applying 0.1M-1M sodium bicarbonate solution in an H-type electrolytic cell at-0.5V-2V relative to the potential of a standard reversible hydrogen electrode, and the figure shows that CO is catalyzed at different potentials after calcination2The faradaic efficiency of formic acid production is obviously improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.

Claims (3)

1. A preparation method of a self-supporting three-dimensional copper-tin alloy material is characterized by comprising the following steps:
(1) preparation of three-dimensional foam copper-tin precursor
Firstly, cleaning the foam copper to remove surface pollutants; dissolving potassium hydroxide and tin dichloride in deionized water to serve as electrolyte, taking the cleaned foamy copper as a working electrode, carrying out constant-current electrolysis in a three-electrode system, washing the working electrode after the electrolysis is finished, and carrying out vacuum drying to obtain a three-dimensional foamy copper tin-based precursor;
(2) preparation of self-supporting three-dimensional copper-tin alloy material
Placing the three-dimensional foam copper tin-based precursor in an inert atmosphere, and heating for reaction to obtain the self-supporting three-dimensional copper-tin alloy material;
in the step (1), the step of cleaning the foamy copper is to perform ultrasonic treatment on the foamy copper in dilute hydrochloric acid, ethanol and deionized water respectively;
in the step (1), the concentration of tin dichloride is 0.01-0.1mol/L and the concentration of sodium hydroxide is 1-3 mol/L;
in the step (1), an Ag/AgCl electrode or a calomel electrode is used as a reference electrode during electrolysis, and a Pt wire or a carbon rod is used as a counter electrode;
in the step (1), the temperature of vacuum drying is 50-70 ℃, and the time is 6-24 h;
in the step (1), the electrolysis time is 1000-3000 s;
in the step (2), the reaction temperature is 200-400 ℃, and the reaction time is 1-4 h.
2. The self-supporting three-dimensional copper-tin alloy material prepared by the preparation method of claim 1.
3. Use of the self-supporting three-dimensional copper-tin alloy material of claim 2 in electrochemical reduction of CO 2.
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