阅读说明：本技术 一种用于电催化还原二氧化碳的铜基纳米材料及其制备方法 (Copper-based nano material for electrocatalytic reduction of carbon dioxide and preparation method thereof ) 是由 王岩 夏帅 张剑芳 吴玉程 余翠平 张勇 于 2021-08-26 设计创作，主要内容包括：本发明公开了一种用于电催化还原二氧化碳的铜基纳米材料及其制备方法,该铜基纳米材料通过一步电化学阳极氧化-阴极沉积工艺制备获得,是在阳极氧化高纯金属铜得到铜离子,与溶液中OH～(-)离子形成[Cu(OH)-(4)]～(2-)络合离子,迁移至阴极电沉积得到铜基纳米材料。本发明的方法简单易操作,所得产物结构新颖、尺寸均匀,用于电催化还原CO-(2)中可实现从甲烷(CH-(4))等C-(1)产物到乙烯(C-(2)H-(4))等C-(2+)产物的转换,且具有较高的选择性和稳定性。(The invention discloses a copper-based nano material for electrocatalytic reduction of carbon dioxide and a preparation method thereof ‑ Ion formation [ Cu (OH) 4 ] 2‑ And (5) complexing ions are transferred to the cathode for electrodeposition to obtain the copper-based nano material. The method is simple and easy to operate, and the obtained product has novel structure and uniform size and is used for electrocatalytic reduction of CO 2 Can be obtained from methane (CH) 4 ) Equal C 1 Product to ethylene (C) 2 H 4 ) Equal C 2+ The product is converted, and has higher selectivity and stability.)

1. A copper-based nanomaterial for electrocatalytic reduction of carbon dioxide, characterized by: the copper-based nano material is prepared by a one-step electrochemical anodic oxidation-cathodic deposition process, wherein high-purity metal copper is subjected to anodic oxidation to obtain copper ions, and the copper ions and OH in solution^-Ion formation [ Cu (OH)₄]^2-And (5) complexing ions are transferred to the cathode for electrodeposition to obtain the copper-based nano material.

2. A method for preparing the copper-based nanomaterial as defined in claim 1, wherein:

in a two-electrode electrolytic cell system, reacting for 0.5-1 hour under the condition of applied voltage by taking high-purity metal copper as an anode, carbon paper as a cathode and potassium hydroxide aqueous solution as electrolyte; and immediately taking out the cathode after the reaction is finished, washing with water, and drying to obtain the copper-based nano material on the cathode.

3. The method of claim 2, wherein: the applied voltage is in the range of 1.5-2.2V.

4. The production method according to claim 2 or 3, characterized in that: the concentration of the potassium hydroxide aqueous solution is 3-6 mol/L.

5. The production method according to claim 2 or 3, characterized in that: the high-purity metal copper is copper foil or a foam copper net.

6. The use of the copper-based nanomaterial of claim 1 in electrocatalytic reduction of carbon dioxide, wherein: in electrocatalytic reduction of CO₂In the process, CO can be realized₂To CH₄And/or CO₂To C₂H₄And (5) converting the product.

Technical Field

The invention relates to the technical field of material science and electrocatalysis, in particular to a method for electrocatalysis reduction of CO₂The copper-based nano material and the preparation method thereof.

Background

With the increasing consumption of three fossil energy sources and the obvious problem of environmental pollution, people are interested in the development and the use of renewable energy sources. The electric energy is used for driving renewable energy sources to be converted into high-value-added fuels and chemical products, and the most possible and realistic effective way for solving the problem of renewable energy source utilization is provided. In addition, large amounts of CO are released with the combustion of fossil fuels₂Gas, which causes the problem of global warming to become more severe. In recent years, CO has been converted electrochemically₂The research on carbon-based fuels and chemicals is widely concerned by researchers. Electrocatalytic reduction of CO₂The process is a combination of renewable power and electrocatalytic process, via CO₂Hydrogenation reactions yield a variety of hydrocarbons, which is a promising carbon recovery technology.

Copper (Cu) is the only one capable of realizing CO₂Electrocatalytic reduction gives the metal as a hydrocarbon product, especially a multi-carbon product. However, copper-based catalysts are used for the electrocatalytic reduction of CO₂In the case of the method, problems such as a high overpotential and low selectivity are often encountered, and the types of products are also widely distributed. Wherein: methane (CH)₄) Is the main component of fuel such as natural gas and coal gasIt can also be used as raw material for preparing hydrogen, carbon black, carbon monoxide, ethynyl formaldehyde and other chemicals, and can be widely used in civil and chemical synthesis. Ethylene (C)₂H₄) Is an important chemical product, is a basic chemical raw material of synthetic fiber, synthetic rubber, synthetic plastic and the like, and the ethylene product plays an important role in national economy. CH (CH)₄And C₂H₄Competing reactions between the products make it difficult to obtain a single product of higher selectivity. At the same time, due to CO₂The competition between the hydrogenation reaction of the reducing intermediates and the hydrogen evolution reaction of the copper electrode leads to CO₂The formation rate of the product converted into the hydrocarbon is low, and the selectivity is poor. Therefore, the copper-based catalyst is reasonably designed and prepared to realize the high-efficiency electrocatalytic reduction of CO₂Production of CH₄Or C₂H₄The research on the products is urgent.

Disclosure of Invention

The invention aims to provide a method for electrocatalytic reduction of CO₂The technical problem to be solved is to prepare the copper-based nano material with single product selectivity so as to realize efficient and stable electro-catalytic reduction of CO₂。

In order to realize the purpose of the invention, the following technical scheme is adopted:

for electrocatalytic reduction of CO₂The copper-based nano material is prepared by a one-step electrochemical anodic oxidation-cathodic deposition process, wherein high-purity metal copper is anodized to obtain copper ions, and the copper ions and OH in solution^-Ion formation [ Cu (OH)₄]^2-And (5) complexing ions are transferred to the cathode for electrodeposition to obtain the copper-based nano material.

The preparation method of the copper-based nano material comprises the following steps:

in a two-electrode electrolytic cell system, reacting for 0.5-1 hour under the condition of applied voltage by taking high-purity metal copper as an anode, carbon paper as a cathode and potassium hydroxide aqueous solution as electrolyte; and immediately taking out the cathode after the reaction is finished, washing with water, and drying to obtain the copper-based nano material on the cathode.

Preferably, the applied voltage is in the range of 1.5-2.2V.

Preferably, the concentration of the potassium hydroxide aqueous solution is 3 to 6 mol/L.

Preferably, the high-purity metal copper is a copper foil or a copper foam net.

The copper-based nano material obtained by the invention grows on the conductive carbon paper in situ and can be directly used for electrocatalytic reduction of CO₂In the electrocatalytic reduction of CO₂In the process, CO can be realized₂To CH₄And/or CO₂To C₂H₄And (5) converting the product.

The electrolyte does not need to be added with any copper source.

Compared with the prior art, the invention has the beneficial effects that:

1. the copper-based nano material with controllable morphology is prepared by a one-step electrochemical anodic oxidation-cathodic deposition process, no complexing agent is required to be added, no copper source is required to be added into electrolyte, the product purity is high, the equipment requirement is low, the experimental operation is simple, and the method is suitable for large-scale production.

2. The copper-based nano material has the advantages of novel structure, uniform size, high purity and unique components.

3. The one-step electrochemical anodic oxidation-cathodic deposition process can realize the synchronous implementation of the anodic oxidation of the metal copper and the cathodic electrodeposition of the divalent copper ions, does not need any copper source and additive, and has short required time.

4. The copper-based nano material grows on the conductive carbon paper and can be directly used as a gas diffusion electrode for electrocatalytic reduction of CO₂In (1).

5. The copper-based nano material is used for electrocatalytic reduction of CO₂In the process, CO can be realized₂To CH₄Product and CO₂To C₂H₄Conversion of the product, CH₄And C₂H₄The local current density of the product can reach 228 and 292mA/cm²The corresponding Faraday efficiencies are 65% and 53%, respectively, and the selectivity and the stability are higher.

Drawings

Fig. 1 is an SEM image of the copper-based nanomaterial prepared in example 1.

Fig. 2 is an SEM image of the copper-based nanomaterial prepared in example 2.

Fig. 3 is an SEM image of the copper-based nanomaterial prepared in example 3.

Fig. 4 is an SEM image of the copper-based nanomaterial prepared in example 4.

Fig. 5 is an SEM image of the copper-based nanomaterial prepared in example 5.

Fig. 6 is an SEM image of the copper-based nanomaterial prepared in example 6.

Fig. 7 is an SEM image of the copper-based nanomaterial prepared in example 7.

Fig. 8 is an SEM image of the copper-based nanomaterial prepared in example 8.

FIG. 9 shows the electrocatalytic reduction of CO by the copper-based nano-materials obtained in the various examples₂Local current density plot of the product.

FIG. 10 shows the electrocatalytic reduction of CO by the copper-based nano-materials obtained in the various examples₂Faradaic efficiency plot of the product.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof will be described in detail with reference to the following examples. The following is merely exemplary and illustrative of the inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the described embodiments by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims defined thereby.

Example 1

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity metal copper foil and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. 3mol/L potassium hydroxide aqueous solution is taken as electrolyte, and the reaction is carried out for 0.5 hour under the condition that the applied voltage is 1.5V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 1 is an SEM image of the target product obtained in this example, and it can be seen that the product is formed by stacking irregular nanoparticles with a particle size of 50-100 nm.

Example 2

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity metal copper foil and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. 3.5mol/L potassium hydroxide aqueous solution is used as electrolyte, and the reaction is carried out for 0.5 hour under the condition that the applied voltage is 1.6V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 2 is an SEM image of the target product obtained in this example, and it can be seen that the product is an octahedral particle stacked nano-mulberry structure with a particle size of 100-200 nm.

Example 3

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity metal copper foil and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. Taking a 4mol/L potassium hydroxide aqueous solution as an electrolyte, and reacting for 0.5 hour under the condition that the applied voltage is 1.7V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

Fig. 3 is an SEM image of the target product obtained in this example, and it can be seen that the product is a nano-mulberry structure with cubic particles stacked, and the particle size is 50-150 nm.

Example 4

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity foamy copper net and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. Reacting for 0.5 hour under the condition that the applied voltage is 1.8V by taking 4.5mol/L potassium hydroxide aqueous solution as electrolyte;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 4 is an SEM image of the target product obtained in this example, and it can be seen that the product is a spherical structure with nanoparticles stacked and the particle size is 30-100 nm.

Example 5

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity foamy copper net and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. 5mol/L potassium hydroxide aqueous solution is used as electrolyte, and the reaction is carried out for 1 hour under the condition that the applied voltage is 1.9V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 5 is an SEM image of the target product obtained in this example, which shows that the product has an irregular polyhedral structure with a size of 300-400 nm.

Example 6

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity metal copper foil and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. 5.5mol/L potassium hydroxide aqueous solution is used as electrolyte, and the reaction is carried out for 1 hour under the condition that the applied voltage is 2.0V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 6 is an SEM image of the target product obtained in this example, which shows that the product has an irregular polyhedral structure with a size of 400-500 nm.

Example 7

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity metal copper foil and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. Taking 6mol/L potassium hydroxide aqueous solution as electrolyte, and reacting for 1 hour under the condition that the applied voltage is 2.1V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂And (5) blowing the carrier by an air gun to obtain the copper-based nano material.

FIG. 7 is an SEM image of the target product obtained in this example, and it can be seen that the surface of the product is of a nanowire structure and has a size of 20-80 nm.

Example 8

In the embodiment, the copper-based nano material is prepared in a two-electrode electrolytic cell system by an electrochemical anodic oxidation-cathodic deposition process, and the specific steps are as follows:

1. respectively adopting a size of 2cm²The high-purity foamy copper net and the carbon paper are used as an anode and a cathode of an electrolytic cell, and the distance between the two electrodes is 3 cm. Taking 6mol/L potassium hydroxide aqueous solution as electrolyte, and reacting for 1 hour under the condition that the applied voltage is 2.2V;

2. immediately taking out the carbon paper of the cathode after the reaction is finished, washing the carbon paper with deionized water for a plurality of times, and then utilizing N₂Air gun blow-drying of carriersAnd obtaining the copper-based nano material.

FIG. 8 is an SEM image of the target product obtained in this example, which shows that the product has a nanorod structure with a size of 50-150 nm.

The copper-based nanomaterials prepared in the above examples 1 to 8 were subjected to electrocatalytic reduction of CO in a flow-type reactor₂Performance test, using 1.0mol/L KOH solution as electrolyte, CO₂The flow rate was set at 20sccm, and the product was quantitatively analyzed by applying a certain voltage and using a gas chromatograph and a nuclear magnetic resonance spectrometer.

Referring to FIGS. 9 and 10, the copper-based nanomaterial obtained from different deposition conditions such as deposition voltage and electrolyte concentration has high efficiency in electrocatalytic reduction of CO₂And the product can be obtained from C by regulating and controlling the deposition voltage₁Product (CH)₄The local current density is 228mA/cm²Faraday efficiency 65%) to C₂₊Product (C)₂H₄The local current density is 292mA/cm²Faradaic efficiency of 53%). Thus, it can be used as an electrocatalytic reduction of CO₂The ideal electrode material.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.