CN114561665B - Ferroelectric modified copper-based electrode with carbon selectivity and preparation method thereof - Google Patents

Ferroelectric modified copper-based electrode with carbon selectivity and preparation method thereof Download PDF

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CN114561665B
CN114561665B CN202210182245.5A CN202210182245A CN114561665B CN 114561665 B CN114561665 B CN 114561665B CN 202210182245 A CN202210182245 A CN 202210182245A CN 114561665 B CN114561665 B CN 114561665B
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copper
zinc oxide
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seed layer
ferroelectric
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CN114561665A (en
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张志成
李丽
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Tianjin University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention relates to an electrocatalytic reduction technology, and belongs to the field of electrochemical materials. The preparation method of the ferroelectric modified copper-based electrode with carbon selectivity comprises the steps of polishing the surface of a copper substrate, carrying out nanocrystallization treatment, growing a zinc oxide seed layer on the surface of the nanocrystallized copper substrate, and finally growing a vanadium-doped zinc oxide nano-sheet array on the surface of the copper substrate with the zinc oxide seed layer, wherein the obtained electrode material is used for catalyzing electrocatalytic reduction of carbon dioxide. The electrode can accelerate the transmission of electrons at the interface of the ferroelectric material and the copper-based catalytic material by utilizing an electric field in the ferroelectric material, thereby improving the catalytic activity of the catalyst in the reduction reaction of carbon dioxide; the electrode has higher electrocatalytic selectivity, can efficiently reduce carbon dioxide molecules in a system, and the prepared product has lower hydrogen content and obviously improves the efficiency of the electrocatalytic reduction of carbon dioxide.

Description

Ferroelectric modified copper-based electrode with carbon selectivity and preparation method thereof
Technical Field
The invention relates to a high-selectivity electrocatalytic material, in particular to a ferroelectric modified copper-based electrode with carbon selectivity and a preparation method thereof.
Background
The electrocatalytic carbon dioxide reduction reaction can convert carbon dioxide into chemical fuels and products with added values by using renewable electric energy, and is a potential energy storage and conversion mode. Electrocatalytic reactions usually occur at the interface of the electrode with the electrolyte solution, involving adsorption of carbon dioxide at the catalyst surface, electron transfer/proton transfer leading to cleavage of carbon-oxygen bonds and formation of carbon-hydrogen bonds, and desorption of the formed end product at the catalyst surface. The carbon dioxide reduction reaction is a multi-step reaction process involving transfer of multiple electrons, so that the variety of reduction products is varied. However, the current electrocatalytic reduction of carbon dioxide still faces the problem of low electron transfer efficiency, and the reason is that the electrode electron transfer potential energy is high, the electron transfer potential energy between the substrate and the electrocatalytic surface is high, and the reaction efficiency of electrode electrons in the electrocatalytic reaction is low; and secondly, the competition reaction of non-carbon particles in the reaction system, particularly the ionization energy of hydrogen ions is low, so that the method has great competition advantage for carbon reduction, and the electric reduction efficiency of carbon dioxide is reduced.
In detail, electron transfer is a key point of the electrocatalytic reduction reaction of carbon dioxide, but at present, the electron transfer speed at the interface still has a problem, the electron transfer speed needs to be improved to promote the formation of products, but the improvement of potential also aggravates the reduction of non-carbon ions, and the efficiency of the whole reaction system is reduced. In the prior art, the water solution system is a low-cost high-efficiency green catalytic system which is preferable for the electrocatalytic reaction, and the reaction system is difficult to replace.
Therefore, the key of ensuring the electrocatalytic reduction process of carbon dioxide is to solve the problem of electrode electron transfer efficiency and reduce non-carbon ions to interfere with reduction reaction.
Disclosure of Invention
The invention aims to solve the technical problems of low efficiency and non-carbon ion interference reduction of the existing electric reduction carbon dioxide by providing a ferroelectric modified copper-based electrode with carbon selectivity.
Technical proposal
A method of making a carbon-selective ferroelectric modified copper-based electrode, the steps comprising:
I. polishing the surface of the copper substrate, and then carrying out nanocrystallization treatment;
II. Growing a zinc oxide seed layer on the surface of the nanocrystallized copper substrate;
III, growing a vanadium doped zinc oxide nano-sheet array on the surface of the copper substrate with the zinc oxide seed layer.
Further, the nanocrystallization step in step I includes: and placing the polished copper foil into a saturated copper sulfate solution for surface copper ion exchange, and drying to obtain cuprous oxide nano particles on the surface of the copper substrate.
Further, the time of the surface copper ion exchange is 1-4 hours; the drying temperature is 70-100 ℃, and the drying time is 2-3 h.
Further, the preparation method of the zinc oxide seed layer in the step II is selected from an electrodeposition method, a spin coating method and a magnetron sputtering method.
Further, when preparing a seed layer by an electrodeposition method, the reaction solution is a hexahydrate zinc nitrate solution, the concentration of the solution is 0.1-1 mol/L, the deposition potential is-1 to-2V, and the deposition time is 10-60 min; when the seed layer is prepared by a spin coating method, the solution is an alcohol solution of zinc acetate, the concentration of the solution is 0.3-0.5 mol/L, the spin coating speed is 800-1500 rpm, and the spin coating times are 10-20 times; when preparing the seed layer by the magnetron sputtering method, the target material is zinc oxide, and the deposition rate of the magnetron sputtering is 1-2 nm/min.
Further, the step of growing the vanadium doped zinc oxide nano-sheet array in the step III includes: and (2) placing the substrate containing the zinc oxide seed layer prepared in the step (II) into a solution of zinc nitrate hexahydrate, hexamethylenetetramine and vanadium pentoxide, and performing a hydrothermal reaction to grow the vanadium-doped zinc oxide nano-sheet array.
Further, the hydrothermal temperature is 80-110 ℃, and the hydrothermal time is 2-5 h.
Further, the polishing method of the copper substrate surface polishing was electrochemical polishing, the polishing rate was 0.1A/cm 2 ～1A/cm 2 The polishing time is 1-15 min, and the concentration of the polishing solution is acid: alcohol is 1:1 to 3:1.
further, the polishing solution is selected from a mixed solution of phosphoric acid and ethylene glycol, or a mixed solution of orthophosphoric acid, ethanol and n-propanol.
A ferroelectric modified copper-based electrode with carbon selectivity comprises a copper substrate, wherein a nano copper layer is arranged on the surface layer of the copper substrate, and a zinc oxide layer is arranged on the surface of the nano copper layer.
Further, the zinc oxide layer comprises a zinc oxide seed layer, and the vanadium doped zinc oxide nano-sheet array is grown on the surface of the zinc oxide seed layer.
A method for electrically reducing carbon dioxide uses the ferroelectric modified copper-based electrode with carbon selectivity as a reducing electrode for electrically reducing carbon dioxide molecules in a solution system.
Advantageous effects
The ferroelectric modified copper-based electrode with carbon selectivity has the following advantages in the electrocatalytic reduction process of carbon dioxide:
1. the ferroelectric modified copper-based electrode with carbon selectivity provided by the invention realizes the recombination of the ferroelectric material and the copper-based catalyst, and can accelerate the transmission of electrons at the interface of the ferroelectric material and the copper-based catalyst by utilizing an electric field in the ferroelectric material, thereby improving the catalytic activity of the catalyst in the reduction reaction of carbon dioxide;
2. the ferroelectric modified copper-based electrode with carbon selectivity has higher electrocatalytic selectivity, can efficiently reduce carbon dioxide molecules in a system, has lower hydrogen content in a prepared product, and remarkably improves the efficiency of the electric reduction of carbon dioxide;
3. the preparation process of the ferroelectric modified copper-based electrode with carbon selectivity is simple, low in cost and pollution-free, can realize large-scale production, and is beneficial to industrial production.
Drawings
FIG. 1 is a cross-sectional view of a carbon-selective ferroelectric modified copper-based electrode according to an embodiment of the present invention;
FIG. 2 is a flow chart of the preparation of a carbon-selective ferroelectric modified copper-based electrode according to the present invention;
FIG. 3 is a scanning electron microscope image of a ferroelectric modified copper-based electrode prepared according to the present invention;
fig. 4 shows the faraday efficiency of the carbon-selective ferroelectric modified copper-based electrode of the present invention for the electro-reduction performance of carbon dioxide.
Detailed Description
The invention will be further illustrated by the following description in conjunction with specific embodiments and figures 1-4
Example 1
The first is a schematic structure of a ferroelectric modified copper-based electrode with carbon selectivity, comprising an electrode material, a nano copper-based catalyst 1, and a ferroelectric material 2 grown on the copper-based catalyst as a substrate.
FIG. two is a flow chart of the preparation of a ferroelectric modified copper-based electrode according to the present invention, comprising the steps of:
(1) Electrochemical polishing of copper foil: commercial copper foil 25 μm thick was subjected to electrochemical polishing, and in this example, the polishing liquid was in a volume ratio of 3:1 with a polishing rate of 0.3A/cm 2 The polishing time was 10min. And (3) flushing the polished copper foil with deionized water to remove the solution on the surface.
(2) Preparation of cuprous oxide nanoparticles: and placing the polished copper foil in a saturated copper sulfate solution, standing for 2 hours, washing with deionized water, and drying in a vacuum drying oven at 80 ℃ for 2 hours.
(3) Preparation of a zinc oxide seed layer: the seed layer can be prepared by spin coating, electrochemical deposition and magnetron sputtering.
In this example, the zinc oxide seed layer was prepared using a spin-on process. Specifically, the ethanol solution of zinc acetate is placed in a water bath kettle at 90 ℃ for heating and dissolving, then is homogenized at the speed of 1000rpm for 60 seconds, and then is placed in a hot table at 150 ℃ for baking for 10 minutes, and the processes of homogenizing, baking and the like are repeated for 10 times.
(4) Preparing vanadium-doped zinc oxide nano-sheets: copper foil wrapped by cuprous oxide nano particles with a zinc oxide seed layer is used as a growth substrate, 25mM zinc nitrate hexahydrate, 5mM vanadium pentoxide and 5mM zinc tetramine are used as hydrothermal solvents, and the reaction is carried out in an oven at 90 ℃ for 1 hour, so that the counter-doped zinc oxide nano sheet array shown in figure 3 is obtained, and the thickness of the counter-doped zinc oxide nano sheet array is 1 mu m.
Example 2
A method for preparing a ferroelectric modified copper-based electrode with carbon selectivity, comprising the following steps:
(1) Electrochemical polishing of copper foil: a commercial copper foil 25 μm thick was electrochemically polished, and in this example, the polishing solution was a mixed solution of 500mL deionized water, 250mL ethanol, 250mL orthophosphoric acid and 50mL isopropyl alcohol. The polishing rate was 1A/cm 2 The polishing time was 1min. And (3) flushing the polished copper foil with deionized water to remove the solution on the surface.
(2) Preparation of cuprous oxide nanoparticles: cuprous oxide nanoparticles were prepared in the same manner as in example 1.
(3) Preparation of a zinc oxide seed layer: in this example, the zinc oxide seed layer was prepared using an electrochemical deposition process. Specifically, a three-electrode system is adopted, a working electrode is copper foil coated with cuprous oxide nano particles, a counter electrode is a platinum sheet electrode, and a reference electrode is a silver/silver chloride electrode. The electrolyte is 0.05mol/L zinc nitrate hexahydrate solution. The deposition potential was-1.2V and the deposition time was 10min.
(4) Preparing vanadium-doped zinc oxide nano-sheets: copper foil wrapped by cuprous oxide nano particles with a zinc oxide seed layer is used as a growth substrate, 25mM zinc nitrate hexahydrate, 1mM vanadium pentoxide and 1mM zinc tetramine are used as hydrothermal solvents, and the reaction is carried out in an oven at 100 ℃ for 3 hours.
Example 3
A method for preparing a ferroelectric modified copper-based electrode with carbon selectivity, comprising the following steps:
(1) Electrochemical polishing of copper foil: the copper foil was electrochemically polished in the same manner as in example 1 or 2.
(2) Preparation of cuprous oxide nanoparticles: cuprous oxide nanoparticles were prepared in the same manner as in example 1 or 2.
(3) Preparation of a zinc oxide seed layer: in this example, the zinc oxide seed layer was prepared using a magnetron sputtering method. Specifically, zinc oxide is used as a target material, the zinc oxide is deposited at a sputtering speed of 1nm/min, the sputtering time is 30min, and the sputtering air flow is 25sccm.
(4) Preparing vanadium-doped zinc oxide nano-sheets: copper foil wrapped by cuprous oxide nano particles with a zinc oxide seed layer is used as a growth substrate, 25mM zinc nitrate hexahydrate, 10mM vanadium pentoxide and hexamethylenetetramine are used as hydrothermal solvents, and the reaction is carried out in an oven at 90 ℃ for 3 hours.
Example 4
A method for preparing a ferroelectric modified copper-based electrode with carbon selectivity, comprising the following steps:
(1) Electrochemical polishing of copper foil: the copper foil was electrochemically polished in the same manner as in example 1 or 2 or 3.
(2) Preparation of cuprous oxide nanoparticles: cuprous oxide nanoparticles were prepared in the same manner as in example 1 or 2 or 3.
(3) Preparation of a zinc oxide seed layer: in this example, the zinc oxide seed layer was prepared using a magnetron sputtering method. Specifically, metal zinc is used as a target, sputtering current is 20mA, and construction time is 20min.
(4) Preparing vanadium-doped zinc oxide nano-sheets: vanadium doped zinc oxide nanoplatelets were prepared using the same method as in example 1 or 2 or 3.
Example 5
Carbon dioxide electrocatalytic reduction experiments were performed based on the carbon-selective ferroelectric modified copper-based electrode prepared in the above examples: electrochemical test is carried out in a sealed H-type electrolytic cell by adopting a three-electrode system, wherein the electrode is used as a working electrode (cathode), a platinum sheet is used as a counter electrode (anode), and Ag/AgCl is used as a reference electrode; meanwhile, the electrolytic cell separates the cathode from the anode by a cation exchange membrane; the electrolyte solution was 0.1M KHCO 3 A solution; the sweep rate of the cyclic voltammogram is 10-100 mV/s; the gas phase product is analyzed by gas chromatography and the liquid phase product is analyzed by liquid chromatography. The electrochemical curves obtained are shown in figure four.
Example 6
The comparative electrode adopts zinc oxide nano-sheet modified copper-based electrode without ferroelectricity, and the specific preparation method is as follows:
(1) Electrochemical polishing of copper foil: the copper foil was electrochemically polished in the same manner as in example 1 or 2 or 3 or 4.
(2) Preparation of cuprous oxide nanoparticles: cuprous oxide nanoparticles were prepared in the same manner as in example 1 or 2 or 3 or 4.
(3) Preparation of a zinc oxide seed layer: in this example, the zinc oxide seed layer was prepared using a magnetron sputtering method. Specifically, metal aluminum is used as a target material, aluminum is deposited at a sputtering speed of 6nm/min, the sputtering time is 5min, and the sputtering air flow is 25sccm.
(4) Preparation of zinc oxide nano-sheets: copper foil wrapped by cuprous oxide nano particles with a zinc oxide seed layer is used as a growth substrate, 25mM zinc nitrate hexahydrate and hexamethylenetetramine are used as hydrothermal solvents, and the reaction is carried out for 3 hours in an oven at 90 ℃.
Discussion: based on the electrocatalytic results of the above embodiment 5, the ferroelectric modified copper-based electrode with carbon selectivity provided by the invention realizes the recombination of the ferroelectric material and the copper-based catalyst, and can accelerate the transmission of electrons at the interface of the ferroelectric material and the copper-based catalyst by utilizing the electric field in the ferroelectric material, thereby improving the catalytic activity of the catalyst in the reduction reaction of carbon dioxide; the ferroelectric modified copper-based electrode with carbon selectivity has higher electrocatalytic selectivity, can efficiently reduce carbon dioxide molecules in a system, has lower hydrogen content in a prepared product, and remarkably improves the efficiency of the electric reduction of carbon dioxide.

Claims (6)

1. A method of making a carbon-selective ferroelectric-modified copper-based electrode, comprising the steps of:
I. polishing the surface of the copper substrate, and then carrying out nanocrystallization treatment;
II, growing a zinc oxide seed layer on the surface of the nanocrystallized copper substrate;
III, growing a vanadium doped zinc oxide nano-sheet array on the surface of the copper substrate with the zinc oxide seed layer;
the nanocrystallization step in the step I comprises the following steps: placing the polished copper foil in a saturated copper sulfate solution for surface copper ion exchange, and drying to obtain cuprous oxide nano particles on the surface of a copper substrate;
the time of the surface copper ion exchange is 1-4 h; the drying temperature is 70-100 ℃, and the drying time is 2-3 h;
the step of growing the vanadium doped zinc oxide nano-sheet array in the step III comprises the following steps: placing the substrate containing the zinc oxide seed layer prepared in the step II into a solution of zinc nitrate hexahydrate, hexamethylenetetramine and vanadium pentoxide, and growing a vanadium-doped zinc oxide nano-sheet array through a hydrothermal reaction;
the hydrothermal temperature is 80-110 ℃, and the hydrothermal time is 2-5 h.
2. The method of preparing a carbon-selective ferroelectric modified copper-based electrode according to claim 1, wherein the preparation method of the zinc oxide seed layer in step II is selected from the group consisting of electrodeposition, spin-coating, and magnetron sputtering.
3. The method for preparing a carbon-selective ferroelectric modified copper-based electrode according to claim 2, wherein when preparing a seed layer by an electrodeposition method, the reaction solution is a hexahydrated zinc nitrate solution with a solution concentration of 0.1-1 mol/L, a deposition potential of-1 to-2V, and a deposition time of 10-60 min; when the seed layer is prepared by a spin coating method, the solution is an alcohol solution of zinc acetate, the concentration of the solution is 0.3-0.5 mol/L, the spin coating speed is 800-1500 rpm, and the spin coating times are 10-20 times; when the seed layer is prepared by a magnetron sputtering method, the target material is zinc oxide, and the deposition rate of the magnetron sputtering is 1-2 nm/min.
4. The method for preparing a carbon-selective ferroelectric modified copper-based electrode according to claim 1, wherein the polishing method for polishing the surface of the copper substrate is selected from electrochemical polishing, and the polishing solution is selected from a mixed solution of phosphoric acid and ethylene glycol, or a mixed solution of orthophosphoric acid and ethanol, n-propanol; the polishing rate was 0.1A/cm 2 ～1 A/cm 2 The polishing time is 1-15 min, and the acid in the polishing solution: alcohol mole is 1-3: 1.
5. a carbon-selective ferroelectric modified copper-based electrode prepared by the method of claim 1, comprising a copper substrate, wherein a nano copper layer is arranged on the surface layer of the copper substrate, a zinc oxide layer is arranged on the surface of the nano copper layer, the zinc oxide layer comprises a zinc oxide seed layer, and a vanadium-doped zinc oxide nano sheet array is grown on the surface of the zinc oxide seed layer.
6. A method for electrocatalytically reducing carbon dioxide, which uses the prepared or protected carbon-selective ferroelectric modified copper-based electrode as a reduction electrode for electrocatalytically reducing carbon dioxide molecules in a solution system.
CN202210182245.5A 2022-02-26 2022-02-26 Ferroelectric modified copper-based electrode with carbon selectivity and preparation method thereof Active CN114561665B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107287615A (en) * 2017-06-01 2017-10-24 北京科技大学 A kind of vanadium doping ZnO nano-rod array light anode and its preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107287615A (en) * 2017-06-01 2017-10-24 北京科技大学 A kind of vanadium doping ZnO nano-rod array light anode and its preparation method and application

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