CN113136597A - Copper-tin composite material and preparation method and application thereof - Google Patents

Copper-tin composite material and preparation method and application thereof Download PDF

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CN113136597A
CN113136597A CN202110264368.9A CN202110264368A CN113136597A CN 113136597 A CN113136597 A CN 113136597A CN 202110264368 A CN202110264368 A CN 202110264368A CN 113136597 A CN113136597 A CN 113136597A
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copper
tin
composite material
nanowires
tin composite
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CN113136597B (en
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鲁统部
霍翠珠
李宇
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Tianjin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a copper-tin composite material and a preparation method and application thereof. The copper-tin composite material takes the copper-tin alloy as a catalytic active substance and can be used as a catalyst, and the copper-tin alloy has a one-dimensional nanowire structure, so that the specific surface area of the catalyst is increased; in addition, the one-dimensional nanowire structure can accelerate charge transfer between the catalyst and the electrolyte, and is favorable for improving current density during electrocatalysis. The invention combines the steps of in-situ synthesis, high-temperature heat treatment and the like, is beneficial to enhancing the binding force between the catalytic active substance and the substrate, reducing the contact resistance, further improving the electrocatalytic current density, and can more effectively catalyze the carbon dioxide reduction and the methanol oxidation.

Description

Copper-tin composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a copper-tin composite material and a preparation method and application thereof.
Background
Fossil fuels have been used as a major source of energy in the past century in power generation and transportation. With the improvement of living standard of people, the increase of the demand of energy sources leads to the increase of fossil fuel consumption, which causes two key problems of (1) the gradual exhaustion of non-renewable fossil energy sources; (2) greenhouse gases produced during the combustion of fossil fuels result in air pollution and climate change.
To address the dual issues of energy crisis and greenhouse gas emissions, the conversion of carbon dioxide into useful chemicals and fuels is a sustainable strategy. The catalytic carbon dioxide reduction method comprises the following steps: the method comprises the steps of photocatalytic carbon dioxide reduction, electrocatalytic carbon dioxide reduction, thermocatalytic carbon dioxide reduction and the like, wherein the electrocatalytic carbon dioxide reduction can utilize renewable energy sources such as solar energy, tidal energy, wind energy and the like as energy sources of a system, and inert carbon dioxide molecules can be catalytically converted into high-value-added chemicals such as formic acid, ethanol and the like under the reaction conditions of normal temperature and normal pressure. Therefore, the electrocatalytic carbon dioxide reduction has good development prospect.
In a traditional electrocatalytic carbon dioxide reduction system, the cathode generates an electrocatalytic carbon dioxide reduction reaction, and the anode generates an oxygen evolution reaction with slow kinetics, resulting in over-potential and over-high overall energy input. In addition, the oxygen product obtained by the oxygen evolution reaction has low added value, and active oxygen species are generated in the process of generating oxygen, and researches show that the active oxygen species can shorten the service life of a proton exchange membrane in the electrolytic cell.
It is therefore of great importance to replace the oxygen evolution reaction at the anode with a thermodynamically more favourable oxidation reaction, which can catalyse the production of high value-added chemicals even at low potentials.
In recent years, researches have proved that substances which can be oxidized, such as methanol, ethanol, urea and the like, are added into an anolyte during the hydrogen production reaction by electrocatalysis, so that the anode potential can be remarkably reduced, and more importantly, the organic small molecules can obtain chemicals with useful values by anodic oxidation. Meanwhile, researches find that the strategy is also suitable for the reaction of the cathode for generating the electrocatalytic carbon dioxide reduction, for example, when Sumit Verma et al electrocatalytic carbon dioxide reduction, the glycerol oxidation reaction is used for replacing the oxygen evolution reaction of the anode, so that 53% of electric energy can be saved, but the research only reduces the potential of the anode and does not analyze the product after the anode oxidation; xinfa Wei et al, using mesoporous tin dioxide grown on carbon cloth and copper oxide nanosheets grown on copper foam as cathode and anode catalysts, respectively, can electrocatalytic carbon dioxide reduction and methanol oxidation to formic acid, respectively, at low cell pressures. However, the method also has the problems of small current density, complicated catalyst preparation and the like. Therefore, there has been an attempt to develop a catalyst which can be used for both the electrocatalytic carbon dioxide reduction reaction and the anode oxidation reaction and can produce high value-added chemicals with high selectivity with low energy consumption.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the copper-tin composite material provided by the invention has good selectivity and catalytic activity on electrocatalytic carbon dioxide.
Meanwhile, the invention also provides a preparation method and application of the copper-tin composite material.
Specifically, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a copper-tin composite material, which comprises a copper substrate and copper-tin alloy nanowires loaded on the copper substrate.
The copper-tin composite material according to the first aspect of the invention comprises at least the following beneficial effects:
according to the invention, the copper-tin alloy nanowire is loaded on the surface of the copper substrate, and the copper-tin alloy can be used as a catalytic active site and has good catalytic activity on electrocatalytic carbon dioxide reduction; meanwhile, the specific surface area of the material is increased by the copper-tin alloy in the form of the nano wire, so that the charge transfer between the copper-tin composite material and the electrolyte can be accelerated in the electrocatalytic carbon dioxide reduction process, the current density is improved, and the catalytic efficiency is further improved.
In some embodiments of the present invention, the mass content of tin in the copper-tin alloy nanowires is 0.7% to 13%.
In some embodiments of the invention, the copper-tin alloy nanowires contain Cu3Sn and Cu6Sn5。
In some embodiments of the present invention, the diameter of the copper-tin alloy nanowire is 200 to 300 nm.
In some embodiments of the present invention, the copper substrate is any one of a copper sheet and a copper foam, preferably a copper foam.
The second aspect of the invention provides a preparation method of the copper-tin composite material, which comprises the following steps:
(1) growing copper hydroxide nanowires in situ on a copper substrate;
(2) heating the copper hydroxide nanowires to obtain copper oxide nanowires;
(3) reducing the copper oxide nanowires into copper nanowires by an electrochemical reduction method;
(4) depositing tin on the copper nanowires;
(5) and (4) calcining the sample obtained in the step (4) to obtain the copper-tin composite material.
The preparation method of the copper-tin composite material according to the second aspect of the invention at least comprises the following beneficial effects:
the inventor finds that if the copper hydroxide nanowires are directly reduced into copper, the obtained copper cannot keep the shape of the nanowires; meanwhile, if a reducing agent is adopted to carry out chemical reduction on the copper hydroxide nanowires or the copper oxide nanowires, the nanowire structure is damaged, and the electrocatalytic performance of the obtained material on carbon dioxide reduction is limited. According to the invention, the copper hydroxide nanowires are converted into the copper oxide nanowires and then subjected to electrolytic reduction to form copper, so that the material can keep the nanowire structure, and the copper-tin alloy can be formed as a catalytic active substance by calcining after tin deposition, so that the copper-tin composite material has good catalytic activity.
In some embodiments of the present invention, in step (1), the copper hydroxide nanowires are prepared by soaking the copper substrate in an alkaline solution, so that the copper hydroxide nanowires can be grown in situ on the copper substrate.
In some embodiments of the invention, the alkaline solution contains a base and an oxidizing agent.
In some embodiments of the invention, the base comprises at least one of sodium hydroxide, potassium hydroxide; the oxidant is persulfate, and comprises at least one of sodium persulfate and ammonium persulfate, and preferably ammonium persulfate.
When the copper substrate is immersed into the alkaline solution, the copper on the surface of the copper substrate is quickly oxidized into Cu by the oxidant2+，Cu2+With OH in alkaline solution-Fast reaction to form monoclinic Cu (OH)2Crystals are deposited on the surface of the copper substrate. Monoclinic Cu (OH)2The nucleation shape of the crystal is generally a rod-shaped structure with a tip, under mild oxidation conditions, most of copper ions are transferred to the tip, so that the crystal grows rapidly in the vertical direction, and only a small part of the crystal grows in the diameter direction, therefore, the nanowire-shaped structure is easily formed. Persulfate oxidizer such as ammonium persulfate exists in solution as peroxodisulfate ion and ammonium ion, wherein peroxodisulfate contains peroxy group, has strong oxidizing property, and can promote copper to be rapidly oxidized into Cu by oxidizer2+. For example, when ammonium persulfate is used as an oxidant and sodium hydroxide is used as a base, the following reaction occurs in the process of preparing the copper hydroxide nanowire: cu +4NaOH + (NH)4)2S2O8→Cu(OH)2+2Na2SO4+2NH3+2H2O。
In some embodiments of the invention, the concentration of the alkali in the alkaline solution is 3 to 6mol/L, preferably 6 mol/L; the mass ratio of the oxidant to the alkali is 1: (3-5).
The dosage of the alkaline solution can be adjusted according to actual needs, and the copper substrate is preferably completely immersed.
In some embodiments of the present invention, the soaking time of the copper substrate in the alkaline solution is 10 to 40 min.
In some embodiments of the present invention, step (1) further includes a step of cleaning the copper substrate, for example, the copper substrate may be immersed in an acetone solution to remove impurities such as grease on the surface, and dilute hydrochloric acid is used to clean the oxide on the surface.
In some embodiments of the invention, in the step (2), the copper hydroxide nanowires are heated to obtain the copper oxide nanowires, specifically, the copper hydroxide nanowires are subjected to heat treatment at 150-350 ℃ in an oxygen-containing atmosphere to obtain the copper oxide nanowires.
In some embodiments of the invention, the oxygen-containing atmosphere is an air atmosphere.
In some embodiments of the present invention, the heat treatment time is 1-2 hours during the preparation of the copper oxide nanowires.
In some embodiments of the invention, in the process of preparing the copper oxide nanowire, the temperature rise rate in the heat treatment process is 5-10 ℃/min.
In some embodiments of the present invention, in step (3), the electrochemical reduction process is specifically that in an electrochemical reduction electrolyte, a copper substrate on which the copper oxide nanowires are grown is used as a working electrode, and constant current reduction is performed.
Compared with a method for reducing by a reducing agent, the reaction from electrochemical reduction of copper oxide to metal copper is quicker, oxygen atoms are quickly lost to enable the surface of the nanowire to be reconstructed, more crystal boundaries are generated, the surface of the copper nanowire is rougher, and more attachment sites are provided for the next step of electrodepositing tin.
In some embodiments of the present invention, the electrochemical reduction electrolyte may adopt a strong alkali weak acid salt solution, such as a sodium bicarbonate solution, a potassium bicarbonate solution, and the like, and the concentration may be set to 0.1 to 0.5 mol/L.
In some embodiments of the invention, the electrochemical reduction electrolyte is free of dissolved oxygen.
In some embodiments of the present invention, the constant current reduction has a current of 3 to 6mA/cm2。
In some embodiments of the present invention, the constant current reduction time is 1-2 h.
In some embodiments of the present invention, the galvanostatic reduction is performed in a three-electrode system, and a common electrode can be used as the reference electrode and the counter electrode, for example, silver/silver chloride can be used as the reference electrode and a platinum sheet can be used as the counter electrode.
In some embodiments of the present invention, in the step (4), the method for depositing tin employs an electrodeposition method.
In some embodiments of the present invention, the electrodeposition method is specifically to perform constant current electrodeposition of tin by using a solution containing tin (II) ions as an electrodeposition electrolyte and a copper substrate on which the copper nanowires are grown as a working electrode. Wherein the tin (II) ion means Sn2+。Sn2+Compare Sn4+Elemental tin is more easily formed by electrodeposition.
In some embodiments of the present invention, the electrodeposition electrolyte contains alkaline substances such as sodium hydroxide and potassium hydroxide, so that the electrodeposition electrolyte is a strongly alkaline solution to prevent tin (II) ions from hydrolyzing to generate precipitates. The concentration of alkaline substances such as sodium hydroxide and potassium hydroxide is 1 to 5mol/L, preferably 2 mol/L.
In some embodiments of the invention, the concentration of tin (II) ions in the electrodeposition electrolyte is 1 to 50 mmol/mL.
In some embodiments of the present invention, the constant current electrodeposition current is 3 to 10mA/cm2。
In some embodiments of the invention, the constant current electrodeposition time is 500 to 3000s, preferably 1000 to 2500 s.
In some embodiments of the present invention, the galvanostatic electrodeposition is performed in a three-electrode system, and a common electrode can be used as the reference electrode and the counter electrode, for example, silver/silver chloride can be used as the reference electrode and a platinum sheet can be used as the counter electrode.
In some embodiments of the present invention, in the step (5), the temperature of the calcination is 260 to 340 ℃.
Before calcination, tin obtained by electrodeposition on the copper nanowire mainly exists in the form of a metallic tin simple substance, and is converted into copper-tin alloy after calcination, so that the bonding force between the active material and the copper substrate is enhanced, and the contact resistance is reduced. In addition, the inventor finds that the current density is higher when electrocatalysis is carried out after calcination, the time for keeping the current density stable is longer, and the Faraday efficiency of anodic oxidation is higher.
In some embodiments of the invention, the heat preservation time at 260-340 ℃ in the calcination process is 2-5 h.
In some embodiments of the present invention, after the calcining, the mixture is cooled to room temperature at a cooling rate of 1-3 ℃/min. In the temperature reduction stage of calcination, the problem of low catalyst repeatability caused by different temperature reduction time due to room temperature change is avoided by controlling the temperature reduction rate.
In some embodiments of the invention, the calcination process is carried out in a mixture of hydrogen and an inert gas. The calcination in the mixed gas containing hydrogen is more beneficial to maintaining the zero valence state of the copper and tin metal to form the alloy.
In some embodiments of the invention, the volume ratio of hydrogen to inert gas is 1: (10-20).
The third aspect of the invention is to provide the application of the copper-tin composite material in preparing an electrode.
A fourth aspect of the invention provides the use of the above copper-tin composite in electrocatalytic carbon dioxide reduction and/or electrocatalytic methanol oxidation.
More specifically, a method of electrocatalytic carbon dioxide reduction comprising the steps of: and electrolyzing the electrolyte into which carbon dioxide is introduced by taking the copper-tin composite material as a cathode.
In some embodiments of the invention, the potential for electrolysis during electrocatalytic carbon dioxide reduction is between-0.8 and-1.5V (vs. In this potential range, the main products of the electrocatalytic carbon dioxide reduction reaction are formic acid, carbon monoxide and hydrogen.
A method of electrocatalytic oxidation of methanol comprising the steps of: and electrolyzing the electrolyte containing the methanol by taking the copper-tin composite material as an anode.
In some embodiments of the invention, the potential of the electrolysis during the electrocatalytic methanol oxidation is 1.4-2.0V (vs. In this potential range, the main product of electrocatalytic oxidation of methanol is formic acid.
A method for simultaneous electrocatalytic carbon dioxide reduction and electrocatalytic methanol oxidation, comprising the steps of: in an electrolyte with carbon dioxide introduced, the copper-tin composite material is taken as a cathode; meanwhile, in an electrolyte containing methanol, another copper-tin composite material is taken as an anode, the cathode is taken as a working electrode, and the anode is taken as a reference electrode and a counter electrode, and the electrolysis is carried out by electrifying.
Compared with the prior art, the invention has the following beneficial effects:
the copper-tin composite material takes the copper-tin alloy as a catalytic active substance and can be used as a catalyst, and the copper-tin alloy has a one-dimensional nanowire structure, so that the specific surface area of the catalyst is increased; in addition, the one-dimensional nanowire structure can accelerate charge transfer between the catalyst and the electrolyte, and is favorable for improving current density during electrocatalysis. The invention combines the steps of in-situ synthesis, high-temperature heat treatment and the like, is beneficial to enhancing the binding force between the catalytic active substance and the substrate, reducing the contact resistance, further improving the electrocatalytic current density, and can more effectively catalyze the carbon dioxide reduction and the methanol oxidation.
Drawings
FIG. 1 shows copper hydroxide nanowires of example 1 [ Cu (OH) ]2NWs]XRD patterns of copper oxide nanowires (CuO NWs) and copper nanowires (Cu NWs);
FIG. 2 is an XRD pattern of CuSn-1, CuSn-2 and CuSn-3;
FIG. 3 is a high resolution scanning electron microscope image of CuSn-1, CuSn-2 and CuSn-3;
FIG. 4 shows the results of performance tests of CuSn-1, CuSn-2, CuSn-3 and copper nanowires (Cu NWs) for electrocatalytic carbon dioxide reduction;
FIG. 5 shows the results of stability testing of CuSn-1 electrocatalytic carbon dioxide reduction;
FIG. 6 is a linear sweep voltammogram of CuSn-1 electrocatalytic methanol oxidation;
FIG. 7 shows the results of performance tests of CuSn-1 electrocatalytic oxidation of methanol to formic acid;
FIG. 8 shows the results of performance tests of CuSn-1 for simultaneous electrocatalytic carbon dioxide reduction and methanol oxidation;
FIG. 9 is a high resolution scanning electron microscope image of CuSn-4, CuSn-5 and CuSn-6;
FIG. 10 shows the results of performance testing of CuSn-4 electrocatalytic carbon dioxide reduction;
FIG. 11 shows the results of performance testing of CuSn-5 electrocatalytic carbon dioxide reduction;
FIG. 12 shows the results of performance testing of CuSn-6 electrocatalytic carbon dioxide reduction;
FIG. 13 is a high resolution scanning electron micrograph of CuSn-7;
FIG. 14 is an XRD pattern of CuSn-7;
FIG. 15 shows the results of performance testing of CuSn-7 electrocatalytic carbon dioxide reduction;
FIG. 16 shows the results of performance tests on the electrocatalytic reduction of carbon dioxide by CuSn-8.
Detailed Description
The technical effects of the present invention will be further described with reference to specific examples.
Example 1
A preparation method of a copper-tin composite material comprises the following steps:
(1) preparation of copper hydroxide nanowires
The area is 1 x 2cm2Commercial copper foam is ultrasonically treated in acetone solution for fifteen minutes to remove impurities such as grease on the surface. 40ml of dilute hydrochloric acid solution with the concentration of 1mol/L is prepared, and the foam copper cleaned in the acetone solution is placed into the prepared dilute hydrochloric acid solution for ultrasonic treatment for fifteen minutes to remove oxides on the surface of the foam copper.
Weighing 1.8g of solid sodium hydroxide particles (6M) and dissolving in 7.5ml of deionized water to prepare a sodium hydroxide solution; 0.4g of ammonium persulfate (0.24M) solid is weighed and dissolved in deionized water to prepare a solution, a sodium hydroxide solution is poured into the ammonium persulfate solution while stirring to obtain a mixed solution, then the cleaned foamy copper is put into the mixed solution and is kept stand for 15 minutes at room temperature, and then the copper hydroxide nanowires can grow on the foamy copper in situ.
(2) Preparation of copper oxide nanowires
And (2) calcining the copper hydroxide nanowires obtained in the step (1) in a tubular furnace, heating to 300 ℃ in air atmosphere (the heating rate is 5 ℃/min), and preserving heat for 3 hours and naturally cooling to room temperature to obtain the copper oxide nanowires.
(3) Preparation of copper nanowires
Reducing the copper oxide nano wire obtained in the step (2) in a three-electrode H-shaped electrolytic cell by constant current, and reducing the copper oxide nano wire by N2Saturated potassium bicarbonate solution is used as electrolyte, the concentration of potassium bicarbonate is 0.1mol/L, and the constant current is set to be 5mA/cm2The reduction time was 5000 s. And (3) taking the foamy copper grown with the copper oxide nanowires obtained in the step (2) as a working electrode, taking silver/silver chloride as a reference electrode and taking a platinum sheet as a counter electrode. And obtaining the copper nanowire on the foam copper after the constant current reduction is finished.
(4) Electrodeposition of tin
Weighing 11.2g of potassium hydroxide solid into 100ml of deionized water, stirring for dissolving, then adding 1128mg of stannous chloride dihydrate for ultrasonic dissolving, taking the foamy copper with the copper nanowires grown obtained in the step (3) as a working electrode, and fixing the area of the working electrode to be 2cm2Silver/silver chloride as reference electrode, platinum sheet as counter electrode, and constant current set at 5mA/cm2The electrodeposition time was 2000 s.
(5) Calcination of
And (3) carrying out heat treatment on the sample obtained in the step (4) in a hydrogen-argon mixed gas (hydrogen: argon is 6: 94, v/v), heating to 300 ℃, keeping the temperature for 3h, controlling the cooling speed to be 1 ℃/min, and cooling to room temperature to obtain the copper-tin composite material, wherein the mark is CuSn-1.
Structural characterization:
copper hydroxide nanowires [ Cu (OH) prepared in steps (1) - (3)2NWs]XRD patterns of the copper oxide nanowires (CuO NWs) and the copper nanowires (Cu NWs) are shown in FIG. 1, XRD pattern of CuSn-1 is shown in FIG. 2, and high-resolution scanning electron micrographs of CuSn-1 are shown in (a) and (d) of FIG. 3. Wherein FIG. 2 shows the presence of Cu in CuSn-13Sn and Cu6Sn5Diffraction peaks related to the alloy phase are shown in (a) and (d) of FIG. 3, and CuSn-1 has a nanowire array structure, and the diameter of the nanowire is 200-300 nm.
As can be seen from FIGS. 1 to 3, the copper hydroxide nanowires, the copper oxide nanowires, the copper nanowires and the copper-tin alloy nanowires are successfully prepared on the copper foam.
Tests show that the copper-tin alloy nanowire in the CuSn-1 contains 7.9 mass percent of tin.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
CuSn-1 was used as a working electrode (the area of the working electrode was fixed at 2 cm)2) Performing an electrocatalytic carbon dioxide reduction performance test in an H-shaped electrolytic cell, wherein silver/silver chloride is used as a reference electrode, and a platinum sheet is used as a counter electrode; in addition, as a comparison, the same performance test was performed with the copper foam grown with copper nanowires (Cu NWs) prepared in step (3) as a working electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electricity (5 coulombs), measuring the Faraday efficiency of liquid-phase formic acid at-1.4V vs. RHE of 87%, gas-phase carbon monoxide of 5%, and hydrogen in balance, and making the current density reach 161mA/cm2. The results of the performance test of CuSn-1 for producing formic acid and carbon monoxide by electrocatalytic carbon dioxide reduction are shown in FIG. 4.
At a current density of 140mA/cm2The results of stability test of electrocatalytic carbon dioxide reduction of CuSn-1 are shown in fig. 5. As can be seen from FIG. 5, CuSn-1 has good stability in the electrocatalytic carbon dioxide reduction process, and the Faraday efficiency of formic acid production is not reduced after long-time testing.
(2) Electrocatalytic oxidation of methanol
The CuSn-1 is used as a working electrode and is carried out in an H-type electrolytic cellAnd (3) testing the performance of the electrocatalytic methanol oxidation, wherein silver/silver chloride is used as a reference electrode, and a platinum sheet is used as a counter electrode. Specifically, in N2Saturated 1mol/L KOH and 1mol/L CH3Electrolyzing with fixed electric quantity in OH mixed solution, measuring the Faraday efficiency of liquid-phase product formic acid to be more than 95% within the voltage range of 1.4-2.0V vs. RHE, generating a small amount of oxygen, and when the voltage is 1.8V vs. RHE, the geometric current density of electrocatalysis methanol oxidation reaches 510mA/cm2. The linear scanning voltammogram and performance test results of electrocatalytic methanol oxidation are shown in fig. 6 and 7, respectively.
(3) Simultaneous electrocatalytic carbon dioxide reduction and methanol oxidation
Two CuSn-1 are respectively used as a cathode and an anode to simultaneously carry out the performance test of electrocatalytic carbon dioxide reduction and methanol oxidation in an H-shaped electrolytic cell, wherein the catholyte is CO2Saturated 0.5mol/L potassium bicarbonate and anolyte N2Saturated 1mol/L KOH and 1mol/L CH3The electrolytic voltage of the OH mixed solution is set as negative voltage, the working electrode is clamped on the working electrode for carbon dioxide reduction, the reference electrode and the counter electrode are clamped on the working electrode for methanol oxidation, and the performance test result is shown in figure 8.
FIG. 8 reflects the faradaic efficiency FE of the cathodic electrocatalytic carbon dioxide reduction in the case of simultaneous electrolysis at both electrodesCO2/HCOOH93.2 percent, the anode electrocatalysis methanol oxidation Faraday efficiency FECH3OH/HCOOHUp to 99.1 percent, and can generate formic acid while achieving high Faraday efficiency.
Comparative example 1
The present comparative example provides a copper-tin composite material, the preparation method of which is different from that of example 1 in that: in the step (4), the amount of stannous chloride dihydrate was reduced to 22.6mg, and the electrodeposition time was set to 50 s. The other operations were the same as in example 1.
The copper-tin composite material obtained in the comparative example was labeled as CuSn-2.
Structural characterization:
an XRD pattern of CuSn-2 is shown in FIG. 2, and high-resolution scanning electron micrographs are shown in (b) and (e) of FIG. 3. As can be seen, CuSn-2 appearsCu3Diffraction peaks associated with Sn alloy phase, no Cu6Sn5The appearance of diffraction peaks associated with the alloy phases; and forming a copper-tin alloy nanowire array structure on the foam copper substrate, wherein the diameter of the nanowire is 200-300 nm.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
And performing an electrocatalytic carbon dioxide reduction performance test in an H-type electrolytic cell by taking CuSn-2 as a working electrode, taking silver/silver chloride as a reference electrode, and taking a platinum sheet as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity, and measuring that the Faraday efficiency of the gas-phase product carbon monoxide is 39% when the voltage is-1.4V vs. RHE, which is improved compared with CuSn-1 in the example 1; the faradaic efficiency of the liquid-phase product formic acid is 38%, which is reduced compared with CuSn-1 in example 1; the rest is hydrogen, and the current density reaches 177mA/cm2The results of the performance test of the electrocatalytic carbon dioxide reduction are shown in fig. 4. The test results of CuSn-2 reflect that, in the copper-tin alloy, along with the reduction of the tin content, the Faraday efficiency of the electrocatalysis of carbon dioxide for reducing formic acid is reduced, and the Faraday efficiency of carbon monoxide is improved.
Comparative example 2
The present comparative example provides a copper-tin composite material, the preparation method of which is different from that of example 1 in that: in the step (4), the electrodeposition time was set to 3000 s. The other operations were the same as in example 1.
The copper-tin composite material obtained in the comparative example was marked as CuSn-3.
Structural characterization:
an XRD pattern of CuSn-3 is shown in FIG. 2, and high-resolution scanning electron micrographs are shown in (c) and (f) of FIG. 3. As can be seen, CuSn-3 is present in addition to Cu3Sn and Cu6Sn5The diffraction peak related to alloy phase also appears, and CuSn-3 has a large number of clusters on the surface of the nanowire array, so that the nanowire array structure is damaged to a certain extent. This reflects that an excessive amount of tin deposition may result from an excessive amount of time in the electrodeposition of tin, which may lead to the destruction of the nanowire array structureBad, and a new SnO phase appears, which may lead to a decrease in current density during electrocatalysis.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
And performing an electrocatalytic carbon dioxide reduction performance test in an H-type electrolytic cell by taking the CuSn-3 as a working electrode, taking silver/silver chloride as a reference electrode, and taking a platinum sheet as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity, and measuring that the faradaic efficiency of liquid phase product formic acid is 74 percent and the faradaic efficiency of gas phase product carbon monoxide is 7.7 percent and the faradaic efficiency of hydrogen is increased to 21 percent when the voltage is-1.4V vs. RHE, and simultaneously reducing the current density to 143mA/cm2The results of the performance test of the electrocatalytic carbon dioxide reduction are shown in fig. 4.
The test results for CuSn-3 reflect that excess tin results in a decrease in current density during electrocatalysis and a decrease in faradaic efficiency for electrocatalysis of carbon dioxide to formic acid.
Comparative example 3
The comparative example provides a copper-tin composite material, and the preparation method of the copper-tin composite material is mainly different from that of the example 1 in that: this comparative example directly electrochemically reduces copper hydroxide nanowires to copper.
Specifically, the preparation method of the copper-tin composite material of the present comparative example includes the steps of:
(1) preparation of copper hydroxide nanowires
This step is the same as step (1) of example 1.
(2) Electrochemical reduction of copper hydroxide nanowires
Reducing the copper hydroxide nano-wire obtained in the step (1) in a three-electrode H-shaped electrolytic cell at constant current, wherein the concentration of potassium bicarbonate in the electrolyte is 0.1mol/L, and the constant current is set to be 5mA/cm2The reduction time was 5000 s. And (2) taking the foamy copper grown with the copper hydroxide nano wire obtained in the step (1) as a working electrode, taking silver/silver chloride as a reference electrode and taking a platinum sheet as a counter electrode.
(3) Electrodeposition of tin
11.2g of potassium hydroxide solid are weighed out to 100mlStirring and dissolving in ionized water, adding 1128mg of stannous chloride dihydrate for ultrasonic dissolution, taking the foamy copper obtained in the step (2) as a working electrode, and fixing the area of the working electrode to be 2cm2Silver/silver chloride as reference electrode, platinum sheet as counter electrode, and constant current set at 5mA/cm2The electrodeposition time was 2000 s.
(4) Calcination of
And (3) carrying out heat treatment on the sample obtained in the step (3) in a hydrogen-argon mixed gas (hydrogen: argon is 6: 94, v/v), heating to 300 ℃, keeping the temperature for 3h, controlling the cooling speed to be 1 ℃/min, and cooling to room temperature to obtain the copper-tin composite material, wherein the mark is CuSn-4.
Structural characterization:
the high resolution scanning electron microscope images of CuSn-4 are shown in fig. 9 (a) and (d), and it can be seen that the nanowire array is damaged and the nanowires are aggregated, which indicates that the nanowire array structure will be damaged by directly performing electrochemical reduction on the copper hydroxide nanowires without being converted into copper oxide nanowires. Meanwhile, a high-resolution scanning electron microscope image obtained in another region of CuSn-4 is shown in (g) of FIG. 9, and the aggregation of nanowires into clusters can also be observed, and the morphology is different from that in (a) of FIG. 9, which further reflects that the nanowires in CuSn-4 are aggregated and the aggregation morphology is not uniform, which indicates that the morphology of the nanowires is uncontrollable by directly performing electrochemical reduction on the copper hydroxide nanowires.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
CuSn-4 is used as a working electrode to perform electrocatalytic carbon dioxide reduction performance test in an H-type electrolytic cell, silver/silver chloride is used as a reference electrode, and a platinum sheet is used as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity at-1.4V vs. RHE. During the test, the current density was found to be 115mA/cm from the beginning2Increased to 130mA/cm in 2 hours2And the current density has a large variation range, as shown in fig. 10, which may be related to the instability of the catalyst structure. Compared with the sample CuSn-1 of example 1, which is subjected to oxidation treatment and re-reduction, the current density of CuSn-4 is obviously reduced, and the Faraday efficiency of formic acid is only that of formic acid32.6 percent, further indicating that the nanowire array structure has the structural advantage of increasing the current density, and the nanowire array structure is more favorable for exposing the catalytic active sites, and improving the performance of electrocatalysis of carbon dioxide to formic acid.
Comparative example 4
The comparative example provides a copper-tin composite material, and the preparation method of the copper-tin composite material is mainly different from that of the example 1 in that: the copper oxide nanowires were reduced using sodium borohydride as a reducing agent.
Specifically, the preparation method of the copper-tin composite material of the present comparative example includes the steps of:
(1) preparation of copper hydroxide nanowires
This step is the same as step (1) of example 1.
(2) Preparation of copper oxide nanowires
This step is the same as step (2) of example 1.
(3) Reduction of copper oxide nanowires
And reducing the copper oxide nanowire by using a reducing agent sodium borohydride. Weighing 2.084g of sodium borohydride (0.5M) and dissolving in 150ml of ultrapure water, ultrasonically dissolving, placing the copper oxide nanowire in the step (2) into the sodium borohydride solution, standing for 2 hours, washing with ultrapure water, and drying.
(4) Electrodeposition of tin
This step is the same as step (4) of example 1.
(5) Calcination of
This step is the same as step (5) of example 1.
The copper-tin composite of this comparative example was labeled CuSn-5.
Structural characterization:
the high resolution scanning electron microscope of CuSn-5 shows that the nanowires are not uniformly dispersed and are staggered and broken as shown in (b) and (e) of fig. 9, which indicates that the reduction of the copper oxide nanowires by using the reducing agent damages the nanowire array structure.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
CuSn-5 is used as a working electrodeAnd (3) carrying out the performance test of electrocatalytic carbon dioxide reduction in an H-shaped electrolytic cell, wherein silver/silver chloride is used as a reference electrode, and a platinum sheet is used as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity at-1.4V vs. RHE. During the test, the current density was found to be 115mA/cm from the beginning2Increased to 157mA/cm in 2 hours2And the current density variation is large, the faraday efficiency of formic acid is only 33%, as shown in fig. 11.
Comparative example 5
The comparative example provides a copper-tin composite material, and the preparation method of the copper-tin composite material is mainly different from that of the example 1 in that: the comparative example adopts reducing agent sodium borohydride to reduce the copper hydroxide nano-wire.
Specifically, the preparation method of the copper-tin composite material of the present comparative example includes the steps of:
(1) preparation of copper hydroxide nanowires
This step is the same as step (1) of example 1.
(2) Reduction of copper hydroxide nanowires
And reducing the copper oxide nanowire by using a reducing agent sodium borohydride. Weighing 2.084g of sodium borohydride (0.5M) and dissolving in 150ml of ultrapure water, ultrasonically dissolving, placing the copper hydroxide nanowire obtained in the step (1) into the sodium borohydride solution, standing for 2 hours, washing with ultrapure water, and drying.
(3) Electrodeposition of tin
This step is the same as step (4) of example 1.
(4) Calcination of
This step is the same as step (5) of example 1.
The copper-tin composite of this comparative example was labeled CuSn-6.
Structural characterization:
as shown in fig. 9 (c) and (f), the high resolution scanning electron microscope of CuSn-6 shows that the nanowire array structure is seriously damaged, collapsed and aggregated into clusters, which indicates that the nanowire array structure is damaged by directly reducing copper hydroxide nanowires into copper by using a reducing agent.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
CuSn-6 is used as a working electrode to perform electrocatalytic carbon dioxide reduction performance test in an H-type electrolytic cell, silver/silver chloride is used as a reference electrode, and a platinum sheet is used as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity at-1.4V vs. RHE. During the test, the current density was found to be 105mA/cm from the beginning2Increased linearly to 132mA/cm in 2 hours2The faradaic efficiency of formic acid was only 31.5%, as shown in figure 12.
Comparative example 6
The comparative example provides a copper-tin composite material, and the preparation method of the copper-tin composite material is mainly different from that of the example 1 in that: this comparative example calcined the sample in a pure argon atmosphere after electrodeposition of tin. The other operations were the same as in example 1.
The copper-tin composite of this comparative example was labeled CuSn-7.
Structural characterization:
the high-resolution scanning electron micrograph of CuSn-7 is shown in FIG. 13, and the XRD map is shown in FIG. 14. As can be seen from FIGS. 13 and 14, although the heat-treated sample of CuSn-7 in high purity argon still maintains the morphology of the nanowire array, except for the presence of Cu in the CuSn-76Sn5And Cu3Besides the diffraction peaks of Sn alloy, the diffraction peaks related to SnO and CuO also appear, which shows that the heat treatment under the pure argon atmosphere is easy to cause the oxidation of copper metal and tin metal which are easy to oxidize.
And (3) testing the electrocatalytic performance:
(1) electrocatalytic carbon dioxide reduction
And performing an electrocatalytic carbon dioxide reduction performance test in an H-type electrolytic cell by taking the CuSn-7 as a working electrode, taking silver/silver chloride as a reference electrode, and taking a platinum sheet as a counter electrode. In particular, in CO2Electrolyzing saturated 0.5mol/L potassium bicarbonate with fixed electric quantity at-1.4V vs. RHE. During the test, the current density was found to be 138mA/cm from the beginning2Reduced to 123mA/cm2Then gradually increased to 140mA/cm2Reason for the current density varying from large to smallIt should be because the oxide on the surface of the catalyst is reduced under the negative potential of carbon dioxide reduction, and the electricity is consumed; meanwhile, the Faraday efficiency of formic acid under the electrocatalysis of CuSn-7 is only 67 percent, as shown in FIG. 15.
Comparative example 7
The comparative example provides a copper-tin composite material, and the preparation method of the copper-tin composite material is mainly different from that of the example 1 in that: this comparative example did not undergo calcination after electrodeposition of tin. The other operations were the same as in example 1.
The copper-tin composite of this comparative example was labeled CuSn-8. The XRD test result of CuSn-8 shows diffraction peaks related to metallic tin.
The electrocatalytic carbon dioxide reduction performance of CuSn-8 was measured in the same manner as in example 1, and the results are shown in fig. 16. The test results reflect that at a potential of-1.4V vs. rhe, the absence of calcination after electrodeposition of tin significantly reduced the faraday efficiency of formic acid, only by about 44%, while the current density was unstable and gradually decreased as the test time was extended.
The results of the performance tests of the electrocatalytic carbon dioxide reduction of CuSn-1 to CuSn-8 are summarized in Table 1 below:
TABLE 1 results of electrocatalytic carbon dioxide reduction performance test
Figure BDA0002971508680000151
Note: the working electrode area was fixed to 2cm during the performance test of each example and comparative example2。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A copper-tin composite material is characterized in that: the copper-tin alloy nanowire array comprises a copper substrate and a copper-tin alloy nanowire loaded on the copper substrate.
2. The copper-tin composite material of claim 1, wherein: in the copper-tin alloy nanowire, the mass content of tin is 0.7-13%.
3. The copper-tin composite material of claim 1, wherein: the copper-tin alloy nanowire contains Cu3Sn and Cu6Sn5。
4. A method for preparing the copper-tin composite material as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) growing copper hydroxide nanowires in situ on a copper substrate;
(2) heating the copper hydroxide nanowires to obtain copper oxide nanowires;
(3) reducing the copper oxide nanowires into copper nanowires by an electrochemical reduction method;
(4) depositing tin on the copper nanowires;
(5) and (4) calcining the sample obtained in the step (4) to obtain the copper-tin composite material.
5. The method for preparing the copper-tin composite material according to claim 4, wherein: in the step (2), the copper hydroxide nanowires are heated to obtain the copper oxide nanowires, specifically, the copper oxide nanowires are subjected to heat treatment at 150-350 ℃ in an oxygen-containing atmosphere to obtain the copper oxide nanowires.
6. The method for preparing the copper-tin composite material according to claim 4, wherein: in the step (3), the electrochemical reduction process is specifically that in an electrochemical reduction electrolyte, a copper substrate on which the copper oxide nanowires grow is used as a working electrode to perform constant current reduction.
7. The method for producing a copper-tin composite material according to claim 4,the method is characterized in that: in the step (4), the method for depositing tin adopts an electrodeposition method; preferably, the electrodeposition method is specifically to contain Sn2+And (4) taking the solution as an electrodeposition electrolyte, taking the copper substrate with the copper nanowires grown obtained in the step (3) as a working electrode, and performing constant-current electrodeposition of tin.
8. The method for preparing the copper-tin composite material according to claim 4, wherein: in the step (5), the calcining temperature is 260-340 ℃; preferably, the calcination process is performed in a mixed gas of hydrogen and an inert gas.
9. Use of the copper-tin composite material according to any one of claims 1 to 3 for the preparation of an electrode.
10. Use of the copper-tin composite material according to any one of claims 1 to 3 in electrocatalytic carbon dioxide reduction and/or electrocatalytic methanol oxidation.
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