CN115595606A - Copper-based catalytic electrode, preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide - Google Patents

Copper-based catalytic electrode, preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide Download PDF

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CN115595606A
CN115595606A CN202211143958.7A CN202211143958A CN115595606A CN 115595606 A CN115595606 A CN 115595606A CN 202211143958 A CN202211143958 A CN 202211143958A CN 115595606 A CN115595606 A CN 115595606A
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palladium
cuprous oxide
catalytic electrode
copper
current collector
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王泽岩
肖涤非
高玉刚
黄柏标
郑昭科
刘媛媛
王朋
程合锋
张倩倩
张晓阳
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/03—Acyclic or carbocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of advanced materials, relates to a carbon dioxide reduction technology, and particularly relates to a copper-based catalytic electrode, a preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide. The catalytic electrode comprises a palladium-cuprous oxide catalyst and a conductive current collector, wherein the palladium-cuprous oxide catalyst is loaded on the surface of the conductive current collector, and the palladium-cuprous oxide catalyst is formed by loading palladium nanoparticles on the surface of cuprous oxide nanoparticles. The palladium-cuprous oxide catalytic electrode disclosed by the invention shows high activity, selectivity to ethylene and stability in preparing ethylene by electrocatalytic reduction of carbon dioxide. Research shows that the performance improvement comes from the fact that palladium can effectively inhibit reduction of monovalent copper and can effectively stabilize CO key intermediates.

Description

Copper-based catalytic electrode, preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide
Technical Field
The invention belongs to the technical field of advanced materials, relates to a carbon dioxide reduction technology, and particularly relates to a copper-based catalytic electrode, a preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Ethylene (C) 2 H 4 ) As an important chemical raw material, carbon dioxide (CO) can be reduced by electrocatalysis 2 ) Thus obtaining the compound. However, electrocatalytic reduction of CO involves numerous cumbersome and complex steps such as C-C coupling 2 Production C 2 H 4 The problems of low selectivity, low activity, poor stability and the like are faced, and the practical application is severely restricted.
To the inventors' study it was realized that copper-based materials are the only ones that can produce C with acceptable efficiency in terms of catalytic electrode materials 2 H 4 The selectivity of the catalytic material is very low, and is only about 40%. Containing monovalent copper (Cu) + ) Of (e.g. cuprous oxide) has a higher pair C 2 H 4 Due to electrocatalytic reduction of CO 2 Very negative operating potential is required, under which condition Cu + Is unstable and is easily reduced to Cu 0 Resulting in a drastic reduction in activity and selectivity。
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a copper-based catalytic electrode, a preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, the copper-based catalytic electrode comprises a palladium-cuprous oxide catalyst and a conductive current collector, wherein the palladium-cuprous oxide catalyst is loaded on the surface of the conductive current collector, and the palladium-cuprous oxide catalyst is formed by loading palladium nanoparticles on the surface of cuprous oxide nanoparticles.
On the other hand, the preparation method of the copper-based catalytic electrode comprises the steps of loading cuprous oxide nanoparticles on the surface of a conductive current collector, and then depositing palladium nanoparticles on the surface of the cuprous oxide nanoparticles by an electrochemical deposition method to obtain the copper-based catalytic electrode;
or depositing the palladium nano particles on the surfaces of the cuprous oxide nano particles by adopting a chemical deposition method or a photochemical deposition method to obtain a palladium-cuprous oxide catalyst, and loading the palladium-cuprous oxide catalyst on the surfaces of the conductive current collectors to obtain the conductive current collector.
In a third aspect, the copper-based catalytic electrode is applied to preparing ethylene by electrocatalytic reduction of carbon dioxide.
The density functional theory shows that the process of preparing ethylene by electrocatalytic reduction of carbon dioxide is complex and needs to undergo 12 steps of electron transfer. In these steps, the two steps of conversion from COOH intermediate to CO intermediate and from two CO intermediates to COCO intermediate are thermodynamic upslopes that require overcoming thermodynamic barriers that are lower for both palladium-cuprous oxide catalysts than for cuprous oxide catalysts. The catalytic electrode based on the palladium-cuprous oxide catalyst is more favorable for preparing ethylene by electrocatalytic reduction of carbon dioxide.
The beneficial effects of the invention are as follows:
the copper-based catalytic electrode provided by the invention is obtained by simple chemical deposition, photochemical deposition or electrochemical deposition, and has the characteristics of simple process, low equipment requirement, easiness in large-scale production and the like.
Experiments show that the copper-based catalytic electrode provided by the invention can realize higher ethylene selectivity, activity and stability in the process of preparing ethylene by electrocatalytic reduction of carbon dioxide; the Faraday efficiency of the catalyst on ethylene can reach 68.5 percent, and the current density can reach 30mA cm -2 And can be kept stable for a long time.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an XRD pattern of cubic cuprous oxide nanoparticles prepared in examples 1-4;
FIG. 2 is an electron microscope picture of cubic cuprous oxide nanoparticles and a palladium-cuprous oxide catalyzed electrode prepared in example 1, a and d are scanning electron microscope pictures of cubic cuprous oxide nanoparticles prepared in example 1, b and e are scanning electron microscope pictures of palladium-cuprous oxide catalyzed electrode prepared in example 1, c and f are transmission electron microscope pictures of palladium-cuprous oxide catalyzed electrode prepared in example 1; g is an EDX spectral surface scan of the palladium-cuprous oxide catalytic electrode prepared in example 1;
FIG. 3 is a photograph of X-ray photoelectron spectroscopy of a palladium-cuprous oxide catalyzed electrode prepared in example 1, a is a fine spectrum of Pd 3d orbital, b is Auger electron spectrum of Cu;
FIG. 4 is a scanning electron micrograph of a palladium-cuprous oxide catalyzed electrode prepared according to example 2, a and c being obtained at a deposition potential of-0.9V vs. RHE, and b and d being obtained at a deposition potential of-1.3V vs. RHE;
FIG. 5 is a scanning electron micrograph of a palladium-cuprous oxide catalyst prepared according to example 3;
FIG. 6 is a scanning electron micrograph of a palladium-cuprous oxide catalyst prepared according to example 4;
fig. 7 is a scanning electron micrograph of the tetradecahedral cuprous oxide nanoparticles prepared in example 5;
FIG. 8 is a scanning electron micrograph of a palladium-cuprous oxide catalyst prepared according to example 5;
FIG. 9 is a graph showing a comparison of selectivity and activity tests for ethylene production by electrocatalytic reduction of carbon dioxide in test example 1, wherein a is a graph showing a comparison of faradaic efficiency of ethylene and b is a graph showing a comparison of partial current density of ethylene;
FIG. 10 is a graph showing a comparison between the stability tests of ethylene produced by electrocatalytic reduction of carbon dioxide in test example 2;
FIG. 11 is a graph showing the change of the surface area ratio of zero-valent copper with time in the case of ethylene production by electrocatalytic reduction of carbon dioxide in the two electrodes in test example 3;
FIG. 12 is a graph showing the structural and morphological changes of the catalyst in experimental example 3 in which two electrodes are used in the production of ethylene by electrocatalytic reduction of carbon dioxide;
fig. 13 is a theoretical simulation diagram of energy for producing ethylene by electrocatalytic reduction of carbon dioxide at two electrodes in test example 4.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the fact that the existing univalent copper needs a very negative operation potential in the process of preparing ethylene by electrocatalytic reduction of carbon dioxide, and the condition easily causes severe reduction of activity and selectivity, the invention provides a copper-based catalytic electrode, a preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide.
In an exemplary embodiment of the present invention, a copper-based catalytic electrode is provided, which includes a palladium-cuprous oxide catalyst and a conductive current collector, wherein the palladium-cuprous oxide catalyst is supported on a surface of the conductive current collector, and the palladium-cuprous oxide catalyst is formed by supporting palladium nanoparticles on a surface of the cuprous oxide nanoparticles.
Researches show that the copper-based catalytic electrode disclosed by the invention has high activity, selectivity and stability to ethylene in the process of preparing ethylene by electrocatalytic reduction of carbon dioxide, and the performance improvement comes from palladium, which can effectively inhibit the reduction of monovalent copper and can effectively stabilize CO key intermediates.
In some embodiments, the conductive current collector includes, but is not limited to, a glassy carbon electrode, carbon paper, carbon cloth, copper foil, copper foam, copper mesh, and the like.
In some embodiments, the loading of palladium nanoparticles in the palladium-cuprous oxide catalyst is 0.2 to 5wt.%.
In some embodiments, the palladium nanoparticle size is 5 to 200nm.
In some embodiments, the cuprous oxide nanoparticles are 20 to 5000nm in size.
In some embodiments, the cuprous oxide nanoparticles have a cubic, octahedral, tetradecahedral, or icosahedral morphology. The electrocatalysis effect of the catalytic electrode formed under the morphology is higher.
The invention provides a preparation method of a copper-based catalytic electrode, which comprises the following steps of loading cuprous oxide nanoparticles on the surface of a conductive current collector, and depositing palladium nanoparticles on the surface of the cuprous oxide nanoparticles by an electrochemical deposition method to obtain the copper-based catalytic electrode;
or depositing the palladium nanoparticles on the surface of the cuprous oxide nanoparticles by adopting a chemical deposition method or a photochemical deposition method to obtain a palladium-cuprous oxide catalyst, and loading the palladium-cuprous oxide catalyst on the surface of the conductive current collector to obtain the conductive current collector.
In some embodiments, when the electrochemical deposition method is used for preparation, cuprous oxide nanoparticles are added into a solvent to prepare an ink, the ink is covered on the surface of the conductive current collector, a pre-catalytic electrode is obtained by drying, and the pre-catalytic electrode is added into an electrolyte containing a palladium source for in-situ electrochemical deposition.
In one or more embodiments, the solvent in which the ink is prepared is an isopropyl alcohol-water-Nafion mixed solution.
In one or more embodiments, the electrolyte is CO 2 Saturated KHCO 3 And (3) solution. The concentration of the potassium bicarbonate water solution is 0.1-0.8 mol/L.
The palladium source is a palladium salt, and in one or more embodiments, the palladium source is an inorganic palladium salt (e.g., palladium nitrate), an inorganic palladate (sodium chloropalladite), diacetonitrile palladium chloride, or bis (ethylene diamine) palladium chloride. The addition amount of the palladium source is that the mass of the palladium is 0.2-10 wt% of the mass of the cuprous oxide nano particles in the pre-catalytic electrode.
In one or more embodiments, the electrochemical deposition potential is from-0.5 to-1.3V vs. RHE; the deposition time is 2 to 30 minutes.
The ink is covered on the surface of the conductive current collector, so that the ink can be dripped on the surface of the conductive current collector, can be coated on the surface of the conductive current collector, and can be coated on the surface of the conductive current collector in a spin coating manner.
In some embodiments, when the chemical deposition method is adopted, cuprous oxide nanoparticles are uniformly dispersed in the dispersant, a palladium source is added, and the palladium-cuprous oxide catalyst is obtained by stirring or ultrasonic reaction for 10 to 120 minutes at room temperature.
In one or more embodiments, the dispersant is water, a water-alcohol solution, a water-dimethylsulfoxide solution. When the dispersant is 20-50 wt.% of water-methanol solution, the dispersion effect is better.
The palladium source is a palladium salt, and in one or more embodiments, the palladium source is an inorganic palladium salt (e.g., palladium nitrate), an inorganic palladate (sodium chloropalladite), diacetonitrile palladium chloride, or bis (ethylene diamine) palladium chloride. The addition amount of the palladium source is that the mass of the palladium is 0.2-10 wt% of the mass of the cuprous oxide nano particles in the pre-catalytic electrode.
In some embodiments, when the photochemical deposition method is adopted, cuprous oxide nanoparticles are uniformly dispersed in the dispersing agent, a palladium source is added, and the palladium-cuprous oxide catalyst is obtained by irradiation for 10-120 minutes by a xenon lamp.
In one or more embodiments, the dispersant is an aqueous solution of a cavitating sacrificial agent. The cavity sacrificial agent can be selected from methanol, triethanolamine and triethylamine, the volume ratio is 5-30%, and sodium sulfite can also be selected, and the concentration is 0.5-5 mol/L.
The palladium source is a palladium salt, and in one or more embodiments, the palladium source is an inorganic palladium salt (e.g., palladium nitrate), an inorganic palladate (sodium chloropalladite), bis-acetonitrile palladium chloride, or bis-ethylene diamine palladium chloride. The addition amount of the palladium source is that the mass of the palladium is 0.2-10 wt% of the mass of the cuprous oxide nano particles in the pre-catalytic electrode.
In some embodiments, the method of supporting the palladium-cuprous oxide catalyst on the surface of the conductive current collector is: adding a palladium-cuprous oxide catalyst into a solvent to prepare ink, covering the surface of the conductive current collector with the ink, and drying.
The choice of solvent and the coverage of the ink is the same as in electrochemical deposition.
In some embodiments, the cuprous oxide nanoparticles are prepared by a wet chemical process comprising the steps of:
adding a copper source, a surfactant and alkali liquor into water at a certain temperature, uniformly mixing, adding a reducing agent under stirring, and reacting to obtain the copper-base catalyst.
The copper source of the present invention is a copper-containing chemical that is intentionally soluble in water, such as copper chloride, copper sulfate, copper nitrate, copper acetate, preferably copper chloride, copper nitrate, or copper acetate.
In one or more embodiments, the temperature is 30 to 75 ℃. Preferably 50 to 60 ℃.
In one or more embodiments, the surfactant can be polyvinylpyrrolidone, dodecyltrimethylammonium, hexadecyltrimethylammonium; preferably polyvinylpyrrolidone; more preferably, the relative molecular mass of polyvinylpyrrolidone is 15000 to 60000.
In one or more embodiments, the base in the lye can be any strong or weak base that is soluble in water; preferably sodium hydroxide or potassium hydroxide.
In one or more embodiments, the reducing agent is citric acid, ascorbic acid, hydroxylamine hydrochloride, or hydrazine hydrate.
In one or more embodiments, the reaction time is from 1 to 10 hours.
The third embodiment of the invention provides an application of the copper-based catalytic electrode in preparing ethylene by electrocatalytic reduction of carbon dioxide.
Specifically, a catalytic electrode is used as the catalytic electrode, and CO is used as the catalytic electrode 2 Saturated KHCO 3 The solution is used as an electrolyte, and the electrocatalytic reduction of carbon dioxide is carried out to prepare ethylene.
In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the technical scheme of the present invention will be described in detail below by combining specific examples and comparative examples. The present invention is not limited to the following examples, which are only simple examples of the present invention and do not represent or limit the scope of the present invention. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
In this embodiment, the palladium-cuprous oxide catalyst supported on the catalyst of the palladium-cuprous oxide catalytic electrode has a structure in which palladium nanoparticles are supported on cuprous oxide nanocubes, and is synthesized by an electrochemical deposition method, specifically:
(1) And (3) synthesizing cubic cuprous oxide nanoparticles: cubic cuprous oxide nanoparticles are synthesized by a wet chemical reduction method. Specifically, 100mL of 0.01M CuNO was added 3 ·2H 2 The aqueous O solution was heated to 55 ℃ in a beaker, after which 10mL of 2M aqueous KOH solution were added dropwise to the solution. After stirring for 30 minutes, 10mL of 0.6M aqueous ascorbic acid solution were added dropwise to the beaker. The mixture was aged at 55 ℃ for 3 hours. Cooling to room temperature, centrifuging to collect precipitate, washing with distilled water and anhydrous ethanol for 3 times, vacuum drying at 60 deg.C for 12 hr to obtain cubic cuprous oxide nanoparticles (c-Cu) 2 O powder. Need toIt is noted that the dropping speeds of the aqueous KOH solution and the aqueous ascorbic acid solution, both of which were 1 drop/sec, had a significant influence on the particle size and uniformity of the final product. For c-Cu 2 Performing phase-to-morphology characterization on the O-powder, and knowing c-Cu through an XRD (X-ray diffraction) spectrum shown in figure 1 2 O powder is pure cuprous oxide with good crystallinity; the C-Cu can be seen from the scanning electron microscope pictures shown in FIG. 2a and FIG. 2d 2 O powder has a uniform, smooth-surfaced, nano-cubic morphology with a diameter of-1 μm.
(2)c-Cu 2 Preparing an O precatalysis electrode: the precatalysed electrode is prepared by reacting c-Cu 2 O powder loading onto a conductive current collector, which in this example is a glassy carbon electrode having a diameter of 5mm. Specifically, 4mg of c-Cu obtained in the step (1) 2 O powder and 6mg of carbon black are ultrasonically dispersed in 0.5mL of isopropanol-water-Nafion mixed solution for 3 hours to obtain uniform catalyst ink. Transferring 6 mu L of catalyst ink drop at the conductive carbon core of the glassy carbon electrode, and naturally airing to obtain the c-Cu 2 O pre-catalytic electrode. The isopropanol-water-Nafion mixed solution is composed of 300 mu L of isopropanol, 150 mu L of distilled water and 50 mu L of Nafion solution, and the concentration of the Nafion solution is 5 percent by weight; in other examples, the isopropyl alcohol-water-Nafion mixed solution was of the composition unless otherwise specified.
(3) Preparing a palladium-cuprous oxide catalytic electrode: the palladium-cuprous oxide catalytic electrode is formed by reaction of c-Cu 2 And carrying out in-situ electrodeposition on Pd nanoparticles on the O precatalysis electrode. Specifically, in a three-electrode system, the c-Cu 2 O pre-catalytic electrode as working electrode and CO 2 Saturated 0.5M KHCO 3 As an electrolyte solution, 10 mu L of palladium source is injected into the electrolyte, and the palladium-cuprous oxide catalytic electrode, recorded as Pd-Cu, is obtained by electrifying for 5 minutes under the deposition potential of-1.1V vs. RHE 2 And O. The palladium source is sodium chloropalladite water solution with the concentration of 1 mM. For the obtained Pd-Cu 2 The morphology and the structure of O are represented, and Pd-Cu can be known from the pictures of a scanning electron microscope and a transmission electron microscope shown in figures 2b and 2e and figures 2c and 2f 2 Palladium-cuprous oxide on O catalyst having palladium with particle size of about 20nmNanoparticles are uniformly loaded on the c-Cu 2 Morphology on O powder; pd-Cu can be known from the X-ray photoelectron spectrum shown in FIG. 3 2 The valence of palladium in the palladium-cuprous oxide on O catalyst is 0 and +2, and the valence of copper is + 1.
Example 2
In this example, the in-situ electrodeposition potential in example 1 was changed. In particular to synthesis of cubic cuprous oxide nano-particles and c-Cu 2 The O precatalysed electrode preparation was the same as step (1) and step (2) in example 1; in the preparation of the palladium-cuprous oxide catalytic electrode, the deposition potential was adjusted to-0.9V vs. RHE and-1.3V vs. RHE instead of-1.1V vs. RHE unlike in step (3) of example 1, and the other method was the same as in step (3) of example 1. The obtained palladium-cuprous oxide catalytic electrode is subjected to morphology characterization, and the scanning electron microscope picture shown in fig. 4 shows that the palladium-cuprous oxide catalyst on the palladium-cuprous oxide catalytic electrode has palladium nanoparticles with the particle size of about 10nm uniformly loaded on the c-Cu 2 The morphology on O, in the picture, the particles with a diameter of 150nm around the nano-cubic block with a diameter of 1 μm are carbon black.
Example 3
In this example, the palladium-cuprous oxide catalyst was synthesized by chemical deposition and then supported on a conductive current collector as a palladium-cuprous oxide catalytic electrode. Specifically, the method comprises the following steps:
(1) Synthesis of cubic cuprous oxide nanoparticles: the same procedure as in (1) the synthesis of cubic cuprous oxide nanoparticles of example 1 was followed, and the product obtained was designated c-Cu 2 O powder。
(2) Synthesizing the palladium-cuprous oxide catalyst by a chemical deposition method: 50mg of the above-mentioned c-Cu 2 Dispersing O powder in 60mL of mixed solution to form uniform dispersion liquid, wherein the mixed solution comprises 40mL of distilled water and 20mL of methanol; adding 1mL of palladium source into the uniform dispersion liquid, wherein the palladium source is PdCl with the concentration of 1mM 2 An aqueous solution; performing ultrasonic reaction in water bath at 20 ℃ for 30min to obtain the Pd-cuprous oxide catalyst synthesized by the chemical deposition method and recorded as Pd-Cu 2 And (4) O-2. For the obtained Pd-Cu 2 O-2 was topographically characterized by the sweep shown in FIG. 5Pd-Cu can be found by scanning electron microscope 2 O-2 with ultrafine palladium nano particles is uniformly loaded on the c-Cu 2 The appearance on O powder, the loading capacity is lower.
(3) Constructing a palladium-cuprous oxide catalytic electrode: in this example, the Pd-cuprous oxide catalytic electrode was prepared by Pd-Cu 2 O-2 is loaded on a conductive current collector. In this embodiment, the conductive current collector is carbon paper, and the area of the carbon paper is 2 × 2cm 2 . Specifically, 5mg of Pd-Cu as described in (2) 2 O-2 and 6mg carbon black were ultrasonically dispersed in 0.5mL isopropanol-water-Nafion mixed solution for 3h to obtain a uniform catalyst ink. 0.4mL of catalyst ink is transferred and coated on carbon paper, and the palladium-cuprous oxide catalytic electrode is obtained after natural airing.
Example 4
In this example, a palladium-cuprous oxide catalyst was synthesized by photochemical deposition and then supported on a conductive current collector as a palladium-cuprous oxide catalytic electrode.
(1) Synthesis of cubic cuprous oxide nanoparticles: the same procedure as in (1) the synthesis of cubic cuprous oxide nanoparticles described in example 1 was followed, and the resulting product was designated c-Cu 2 O powder。
(2) Synthesizing a palladium-cuprous oxide catalyst by a photo-deposition method: 20mg of the above-mentioned c-Cu 2 Dispersing O powder in 60mL of mixed solution to form uniform dispersion liquid, wherein the mixed solution consists of 40mL of acetonitrile and 20mL of methanol; adding 0.5mL of palladium source into the uniform dispersion liquid, wherein the palladium source is a 1mM diacetonitrile palladium chloride aqueous solution; performing full light irradiation with 300W xenon lamp in water bath at 15 deg.C for 30min to obtain Pd-cuprous oxide catalyst, named Pd-Cu, synthesized by photochemical deposition method 2 And (4) O-3. For the obtained Pd-Cu 2 The appearance of the O-3 is characterized, and Pd-Cu can be known from the scanning electron microscope picture shown in figure 6 2 O-3 Palladium nanoparticles having a diameter of about 20nm are uniformly supported on the above-mentioned c-Cu 2 Morphology on O powder.
(3) Constructing a palladium-cuprous oxide catalytic electrode: in this example, the Pd-cuprous oxide catalytic electrode was prepared from Pd-Cu 2 O-3 is loaded on a conductive current collector. In this embodiment, the conductive current collector is a copper foilArea of 2 x 2cm 2 . Specifically, 5mg of Pd-Cu as described in (2) 2 O-2 and 6mg carbon black were ultrasonically dispersed in 0.5mL isopropanol-water-Nafion mixed solution for 3h to obtain a uniform catalyst ink. 0.4mL of catalyst ink is transferred and coated on carbon paper, and the palladium-cuprous oxide catalytic electrode is obtained after natural airing.
Example 5
In this example, the palladium-cuprous oxide catalyst supported on the catalyst of the palladium-cuprous oxide catalytic electrode has a structure in which palladium nanoparticles are supported on a cuprous oxide nanotetrahedron, and is synthesized by a photochemical deposition method, specifically:
(1) Synthesis of tetradecahedron cuprous oxide nanoparticles: synthesizing the tetradecahedron cuprous oxide nano-particles by a wet chemical reduction method. Specifically, 100mL of the solution contains 0.01M CuNO 3 ·2H 2 O and 4g of an aqueous solution of PVP with a relative molecular mass of 28000 were heated to 55 ℃ in a beaker, and 10mL of a 2M aqueous KOH solution were added dropwise to the solution. After stirring for 30 minutes, 10mL of 0.6M aqueous ascorbic acid solution were added dropwise to the beaker. The mixture was aged at 55 ℃ for 3 hours. Cooling to room temperature, centrifuging to collect precipitate, washing with distilled water and anhydrous ethanol for 3 times, vacuum drying at 60 deg.C for 12h to obtain tetrakaidecahedral cuprous oxide nanoparticles (t-Cu) 2 O powder. It should be noted that the dropping speeds of the aqueous KOH solution and the aqueous ascorbic acid solution significantly affect the particle size and uniformity of the final product, and in this example, both the dropping speeds of the aqueous KOH solution and the aqueous ascorbic acid solution are 1 drop/second. For t-Cu 2 O is subjected to morphology characterization, and t-Cu can be obtained from the scanning electron microscope picture shown in figure 7 2 O powder has a uniform, smooth-surfaced, nano-tetradecahedron shape with a diameter of 1 μm.
(2) Synthesizing a palladium-cuprous oxide catalyst by a photo-deposition method: 20mg of the above t-Cu 2 Dispersing O powder in 60mL of mixed solution to form uniform dispersion liquid, wherein the mixed solution consists of 40mL of acetonitrile and 20mL of methanol; adding 0.5mL of palladium source into the uniform dispersion liquid, wherein the palladium source is a 1mM diacetonitrile palladium chloride aqueous solution; performing all-optical irradiation for 30min in a water bath at 15 ℃ by using a 300W xenon lamp to obtain the product synthesized by the photochemical deposition methodPalladium-cuprous oxide catalyst, designated Pd-Cu 2 And (4) O-4. For the obtained Pd-Cu 2 The appearance of O-4 is characterized, and Pd-Cu can be known from the scanning electron microscope picture shown in figure 8 2 O-4 having palladium nanoparticles with a diameter of about 40nm was uniformly supported on the above t-Cu 2 Morphology on O powder.
(3) Constructing a palladium-cuprous oxide catalytic electrode: in this example, the Pd-cuprous oxide catalytic electrode was prepared from Pd-Cu 2 O-4 is loaded on a conductive current collector. In this embodiment, the conductive current collector is carbon paper, and the area of the copper foil is 2 × 2cm 2 . Specifically, 5mg of Pd-Cu as described in (2) 2 O-4 and 6mg of carbon black were ultrasonically dispersed in 0.5mL of an isopropanol-water-Nafion mixed solution for 3 hours to obtain a uniform catalyst ink. 0.4mL of catalyst ink is transferred and dripped on carbon paper, and the palladium-cuprous oxide catalytic electrode is obtained after natural airing.
Comparative example 1
To better illustrate the beneficial effects of the palladium-cuprous oxide catalyst and palladium-cuprous oxide catalytic electrode of the present invention in the electrocatalytic reduction of carbon dioxide to ethylene, c-Cu as described in example 1 was used 2 c-Cu with O powder loaded on conductive current collector 2 The O precatalysed electrode is directly used as a catalytic electrode and is marked as c-Cu 2 And (O). Specifically, the method comprises the following steps:
(1) Synthesis of cubic cuprous oxide nanoparticles: the same procedure as in (1) the synthesis of cubic cuprous oxide nanoparticles described in example 1 was followed, and the resulting product was designated c-Cu 2 O powder。
(2)c-Cu 2 Preparing an O catalytic electrode: c-Cu 2 The O-catalyzed electrode is prepared by mixing c-Cu 2 O powder loading onto a conductive current collector, which in this example is a glassy carbon electrode having a diameter of 5mm. Specifically, 4mg of c-Cu as described in (1) 2 O powder and 6mg of carbon black are ultrasonically dispersed in 0.5mL of isopropanol-water-Nafion mixed solution for 3 hours to obtain uniform catalyst ink. Transferring 6 mu L of catalyst ink drop to the conductive carbon core of the glassy carbon electrode, and naturally airing to obtain the c-Cu 2 O catalytic electrode, noted c-Cu 2 O。
Test example 1
To demonstrate the beneficial effects of the palladium-cuprous oxide catalytic electrode of the present invention on the electrocatalytic reduction of carbon dioxide to ethylene, the Pd-Cu as described in example 1 was tested and compared in this experimental example 2 O and c-Cu as described in comparative example 1 2 Selectivity and activity of preparing ethylene by electrocatalytic reduction of carbon dioxide by O. Specifically, the method comprises the following steps:
in a three-electrode system with CO 2 Saturated 0.5M KHCO 3 The aqueous solution is used as electrolyte, the Ag/AgCl electrode is used as reference electrode, and Pd-Cu is used respectively 2 O and c-Cu 2 O as working electrode, test Pd-Cu 2 O and c-Cu 2 The yield of ethylene at different potentials was determined and the faradaic efficiency of ethylene and the ethylene fractional current density were calculated. Pd-Cu as shown in FIG. 9a 2 The highest ethylene Faraday efficiency of O at-1.1V vs. RHE reaches 63.8 percent, and Pd-Cu 2 O has higher selectivity to ethylene than c-Cu at all potentials 2 And (O). Shows that the Pd-Cu of the invention 2 O higher ethylene production selectivity. As shown in FIG. 9b, pd-Cu at all potentials 2 The ethylene current density of O is higher than that of c-Cu 2 O, pd-Cu at a potential of-1.1V vs. RHE 2 Ethylene partial current density of O is c-Cu 2 1.8 times of O. Shows that the Pd-Cu of the invention 2 O higher ethylene production activity.
Test example 2
In this test example, pd-Cu described in example 1 2 O and c-Cu as described in comparative example 1 2 The stability of ethylene produced by electrocatalytic reduction of carbon dioxide with O was tested. Specifically, the method comprises the following steps:
in a three-electrode system with CO 2 Saturated 0.5M KHCO 3 The aqueous solution is used as electrolyte, the Ag/AgCl electrode is used as reference electrode, and Pd-Cu is respectively used 2 O and c-Cu 2 And O is used as a working electrode, and long-time electrolysis tests are carried out to test the stability of the O. As shown in FIG. 10, pd-Cu 2 O is able to maintain stable current density and ethylene selectivity over a 35 hour electrolysis process. However, c-Cu 2 The activity of O sharply decreases after the start of electrolysis, the selectivity to ethylene also sharply decreases, and electrolysis 1The selectivity to ethylene declined to-30% after 0 hours. Shows that the Pd-Cu of the invention 2 The stability of preparing ethylene by electrocatalytic reduction of carbon dioxide is obviously improved.
Test example 3
The purpose of this experimental example is to enhance the understanding of the improved stability of the palladium-cuprous oxide catalyzed electrode. Specifically, the method comprises the following steps:
in a three-electrode system with CO 2 Saturated 0.5M KHCO 3 The aqueous solution is used as electrolyte, the Ag/AgCl electrode is used as reference electrode, and Pd-Cu is respectively used 2 O and c-Cu 2 And O is used as a working electrode, the content of zero-valent copper on the surface of the electrode is measured when the electrolysis time is 1, 3 and 8 hours, the proportion of the zero-valent copper to all copper is calculated, and the appearance of the catalyst in the electrode is observed. As shown in FIG. 11, the zero-valent copper was in Pd-Cu at all times 2 The proportion of O is obviously lower than that of c-Cu 2 The proportion of O indicates that the load of palladium effectively inhibits the reduction of cuprous oxide. As shown in FIG. 12, in the electrolytic process, c-Cu 2 O suffers significant structural damage during electrolysis, while Pd-Cu 2 O can maintain its own structure. These show that the Pd-Cu of the present invention 2 The stability of the ethylene prepared by electrocatalytic reduction of carbon dioxide with obviously improved O lies in Pd-Cu 2 The structural stability of O is obviously improved, and further shows that the palladium can effectively protect cuprous oxide and inhibit monovalent copper from being reduced.
Test example 3
In this test example, pd-Cu as described in example 3 2 Catalytic electrode comprising O-2 catalyst, pd-Cu as described in example 4 2 Catalytic electrode comprising O-3 catalyst, pd-Cu as described in example 5 2 The selectivity of the electro-catalysis of carbon dioxide to ethylene by a catalytic electrode consisting of an O-4 catalyst was tested. Their highest faradaic efficiencies for ethylene reached 61.2%, 65.5%, 68.5%, respectively. The palladium-cuprous oxide catalytic electrode has high selectivity of preparing ethylene by electrocatalytic reduction of carbon dioxide.
Test example 4
In this test example, the electrocatalytic reduction of dioxygen by the palladium-cuprous oxide catalytic electrode according to the present inventionThe carbon-to-ethylene process was theoretically simulated by density functional theory in order to help those skilled in the art better understand the improved ethylene selectivity of the palladium-cuprous oxide catalyzed electrode of the present invention. As shown in fig. 13, the process of preparing ethylene by electrocatalytic reduction of carbon dioxide is complicated and requires 12 steps of electron transfer. In these steps, the two steps of conversion from the COOH intermediate to the CO intermediate and from the two CO intermediates to the COCO intermediate are thermodynamically upsloped processes requiring overcoming the thermodynamic barrier, in which the Pd — Cu intermediate is present 2 The thermodynamic barriers of O are all lower than that of c-Cu 2 The thermodynamic barrier to O. The palladium-cuprous oxide catalytic electrode is more favorable for preparing ethylene by electrocatalytic reduction of carbon dioxide.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The copper-based catalytic electrode is characterized by comprising a palladium-cuprous oxide catalyst and a conductive current collector, wherein the palladium-cuprous oxide catalyst is loaded on the surface of the conductive current collector, and the palladium-cuprous oxide catalyst is formed by loading palladium nanoparticles on the surface of cuprous oxide nanoparticles.
2. The copper-based catalytic electrode of claim 1, wherein the palladium nanoparticles loading in the palladium-cuprous oxide catalyst is 0.2-5 wt.%.
3. The copper-based catalytic electrode of claim 1, wherein the cuprous oxide nanoparticles have a cubic, octahedral, tetradecahedral, or icosahedral morphology.
4. A preparation method of a copper-based catalytic electrode is characterized in that cuprous oxide nano-particles are loaded on the surface of a conductive current collector, and then palladium nano-particles are deposited on the surface of the cuprous oxide nano-particles by an electrochemical deposition method to obtain the copper-based catalytic electrode;
or depositing the palladium nanoparticles on the surface of the cuprous oxide nanoparticles by adopting a chemical deposition method or a photochemical deposition method to obtain a palladium-cuprous oxide catalyst, and loading the palladium-cuprous oxide catalyst on the surface of the conductive current collector to obtain the conductive current collector.
5. The method for preparing the copper-based catalytic electrode according to claim 4, wherein the copper-based catalytic electrode is prepared by an electrochemical deposition method, the cuprous oxide nanoparticles are added into a solvent to prepare ink, the ink is covered on the surface of the conductive current collector, the pre-catalytic electrode is obtained by drying, and the pre-catalytic electrode is added into an electrolyte containing a palladium source for in-situ electrochemical deposition.
6. The preparation method of the copper-based catalytic electrode as claimed in claim 4, wherein the chemical deposition method is adopted, the cuprous oxide nanoparticles are uniformly dispersed in the dispersant, the palladium source is added, and the palladium-cuprous oxide catalyst is obtained by stirring or ultrasonic reaction at room temperature for 10-120 minutes.
7. The preparation method of the copper-based catalytic electrode as claimed in claim 4, wherein the method comprises dispersing cuprous oxide nanoparticles in the dispersant uniformly by photochemical deposition, adding palladium source, and irradiating with xenon lamp for 10-120 min to obtain the palladium-cuprous oxide catalyst.
8. The method for preparing the copper-based catalytic electrode according to claim 4, wherein the method for supporting the palladium-cuprous oxide catalyst on the surface of the conductive current collector comprises the following steps: adding a palladium-cuprous oxide catalyst into a solvent to prepare ink, covering the surface of the conductive current collector with the ink, and drying.
9. The use of a copper-based catalytic electrode according to any one of claims 1 to 3 or a copper-based catalytic electrode prepared by the preparation method according to any one of claims 4 to 8 in the preparation of ethylene by electrocatalytic reduction of carbon dioxide.
10. Use according to claim 9, characterized in that a copper-based catalytic electrode is used as catalytic electrode, and CO is used as catalytic electrode 2 Saturated KHCO 3 The solution is used as an electrolyte to carry out electrocatalytic reduction on carbon dioxide to prepare ethylene.
CN202211143958.7A 2022-09-20 2022-09-20 Copper-based catalytic electrode, preparation method and application thereof in preparing ethylene by electrocatalytic reduction of carbon dioxide Pending CN115595606A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07112945A (en) * 1993-10-15 1995-05-02 Sumitomo Metal Ind Ltd Conversion of carbon dioxide
CN103977814A (en) * 2014-05-14 2014-08-13 中国科学技术大学 Size-controllable palladium-cuprous oxide nano catalyst as well as preparation method and catalysis application of catalyst
WO2016041405A1 (en) * 2014-09-15 2016-03-24 中国科学院深圳先进技术研究院 Pd-BASED COMPOSITE NANOPARTICLE AND PREPARATION METHOD THEREFOR
CN108479855A (en) * 2018-03-28 2018-09-04 北京工业大学 A kind of nucleocapsid metal organic framework base composite photocatalyst and preparation method thereof
CN111118601A (en) * 2019-12-23 2020-05-08 山东大学 Catalyst, electrode and method for preparing ethylene by carbon dioxide reduction
CN111841568A (en) * 2020-07-02 2020-10-30 广州大学 Preparation and application of cuprous oxide loaded Pd composite photocatalytic material for photocatalytic reduction of carbon dioxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07112945A (en) * 1993-10-15 1995-05-02 Sumitomo Metal Ind Ltd Conversion of carbon dioxide
CN103977814A (en) * 2014-05-14 2014-08-13 中国科学技术大学 Size-controllable palladium-cuprous oxide nano catalyst as well as preparation method and catalysis application of catalyst
WO2016041405A1 (en) * 2014-09-15 2016-03-24 中国科学院深圳先进技术研究院 Pd-BASED COMPOSITE NANOPARTICLE AND PREPARATION METHOD THEREFOR
CN108479855A (en) * 2018-03-28 2018-09-04 北京工业大学 A kind of nucleocapsid metal organic framework base composite photocatalyst and preparation method thereof
CN111118601A (en) * 2019-12-23 2020-05-08 山东大学 Catalyst, electrode and method for preparing ethylene by carbon dioxide reduction
CN111841568A (en) * 2020-07-02 2020-10-30 广州大学 Preparation and application of cuprous oxide loaded Pd composite photocatalytic material for photocatalytic reduction of carbon dioxide

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