CN113789528B - Copper catalyst with carbon substrate loaded with different morphologies and application thereof - Google Patents
Copper catalyst with carbon substrate loaded with different morphologies and application thereof Download PDFInfo
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- CN113789528B CN113789528B CN202111160896.6A CN202111160896A CN113789528B CN 113789528 B CN113789528 B CN 113789528B CN 202111160896 A CN202111160896 A CN 202111160896A CN 113789528 B CN113789528 B CN 113789528B
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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
- C25B3/00—Electrolytic production of organic compounds
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- C25B3/07—Oxygen containing compounds
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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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
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- C25B3/29—Coupling reactions
Abstract
The invention discloses a copper catalyst with different morphologies loaded on a carbon substrate and application thereof, belonging to the technical field of electrochemical synthesis and catalysis. By controlling the potential of the electrodeposition, the reduction speed of copper ions on the carbon substrate is changed, and the morphology and the chemical state of the copper simple substance loaded on the carbon substrate are further influenced. The copper with the micro-tower-shaped morphology is used as the catalyst, has excellent catalytic performance for electrochemical coupling reaction of electrochemically fixed carbon dioxide and epoxy compounds, effectively improves the selectivity and yield of target products of cyclic ester compounds, has high stability, is convenient to prepare and low in cost, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of electrochemical synthesis and catalysis, in particular to a copper catalyst with different morphologies loaded on a carbon substrate and application thereof.
Background
The carbon dioxide which causes the greenhouse effect is converted into chemicals and fuels, and the concept of environmental protection and sustainable development is met. Coupling carbon dioxide with other compounds to higher value added compounds (e.g., carboxylic acids, ureas, carbamates, carbonates, etc.) is a means of maximizing the benefit of fixed storage of carbon dioxide compared to basic chemicals that are converted to carbon monoxide, methanol, etc. Currently, the coupling of carbon dioxide and an epoxy compound to form a five-membered cyclic carbonate is considered one of the most important reactions for carbon dioxide fixation. The cyclic carbonate can be used as a battery electrolyte, a green reagent and a fuel additive, and can be polymerized into novel degradable material polycarbonate.
At present, the cyclic carbonate is coupled mainly by a traditional thermocatalytic reaction system, a metal organic framework catalyst, an ionic liquid catalyst, a non-metal organic catalyst and the like are required in the process, the production cost of the catalysts is high, and the preparation method is complex, so that the practical application of the catalysts is greatly restricted. Under severe reaction conditions (> 1MPa, >80 ℃) causes great energy resource consumption.
The electrochemical coupling carbon dioxide and epoxy compound catalytic system can take electric energy instead of internal energy as a driving force, can be carried out at normal temperature and normal pressure, and obtains excellent catalytic performance by taking copper loaded on a carbon substrate as a catalyst. The catalyst has smaller crystal grains and larger specific surface area, so that the catalyst contains abundant electrochemical active sites, and the epoxy compound has excellent conversion and the carbonate compound has larger yield. The copper catalyst has great potential application value in the field of synthesis of cyclic carbonate due to the cheap preparation materials and the simple preparation process.
Disclosure of Invention
The invention aims to provide a copper catalyst with different morphologies supported on a carbon substrate and application thereof. By optimizing the reaction conditions, the reaction system can be carried out at normal temperature and normal pressure, and has the characteristics of low energy consumption and simple and convenient reaction conditions.
The technical scheme of the invention is as follows:
the copper catalyst is loaded on the carbon substrate, and the microscopic morphology of the copper catalyst is granular, tower-shaped or flower-shaped.
The particle size of the granular copper is 1-2 mu m, the particle size of the pinecone-shaped copper is 70-90 nm, and the particle size of the flower-shaped copper is 40-60 nm.
The carbon substrate is a carbon material composed of carbon fibers, such as carbon paper, carbon cloth, and the like.
The copper catalyst with different morphologies loaded on the carbon substrate is prepared by an electrodeposition method, and the preparation method comprises the following steps:
(1) Preparing a copper salt solution with the concentration of 0.05-0.2 mol/L as an electrolyte, wherein the copper salt solution is a copper sulfate solution or a copper chloride solution;
(2) The copper catalyst is prepared by electrodeposition on a carbon substrate, the electrodeposition is carried out in a three-electrode system of a single electrolytic cell, a working electrode is the carbon substrate, a counter electrode is a platinum wire, a platinum sheet or a platinum net, a reference electrode is a silver/silver chloride, hydrogen electrode, calomel electrode or mercury/mercury oxide electrode, the electrodeposition is carried out by a constant-pressure or constant-current method, and the deposition time is 2-20 min.
In the step (2), when the constant voltage method is used for electrodeposition, the constant voltage used for preparing the copper nanoparticle catalyst with the granular microscopic morphology is 0.4-0.1V RHE (ii) a The constant voltage used for preparing the copper catalyst with the microcosmic appearance of the pinecone is-1.0 to-0.7V RHE (ii) a The constant voltage used for preparing the copper catalyst with the micro-morphology of flower shape is-1.5 to-1.2V RHE 。
The copper catalyst is applied to electrochemical catalytic reaction for electrochemically fixing carbon dioxide and performing addition reaction on an epoxy compound.
The electrochemical catalytic reaction is carried out in a three-electrode system of an H-shaped electrolytic cell, and an epoxy compound and carbon dioxide are coupled to synthesize an ester compound (five-membered cyclic carbonate); in the three-electrode system, ag/AgCl is used as a reference electrode and is arranged in a cathode pool, a platinum sheet is used as a counter electrode and is arranged in an anode pool, a copper catalyst and an epoxy compound are arranged in the cathode pool, the cathode pool and the anode pool are separated by a proton exchange membrane, electrolyte solutions are filled in the cathode pool and the anode pool, and the electrolyte solutions consist of: an electrolyte, a cocatalyst and an organic solvent; continuously and stably introducing CO into the cathode pool 2 And carrying out electrochemical reduction under the condition of constant pressure or constant current.
In the electrochemical catalytic reaction system, an organic solvent is acetonitrile, DMF or dioxane, an electrolyte is zinc chloride, and a cocatalyst is tetrabutylammonium bromide; the epoxy compound is one or more of epoxypropane, epichlorohydrin, epoxy cyclohexane and epoxy styrene.
In the galvanic coupling reaction of carbon dioxide and epoxy compound, the concentration of electrolyte zinc chloride in the reaction system is 0.015-0.045 mol/l, the concentration of cocatalyst tetrabutylammonium bromide is 0.045-0.135 mol/l, the conversion rate of the epoxy compound is 92-95%, and the yield of the ester compound is 74-80%.
The principle of the invention is as follows:
the organic solvent in the invention is acetonitrile, DMF and dioxane, can dissolve the electrolyte and the cocatalyst, and provides an anhydrous environment for coupling the epoxy compound and carbon dioxide into the cyclic carbonate. The zinc chloride in the system is used as electrolyte, so that the resistance of the system can be effectively reduced, most of migration current is borne, and the influence of migration on the mass transfer of electrochemical active substances is eliminated.
The substrate of the catalyst in the invention is carbon paper composed of a plurality of carbon fibers, and the electron transfer speed on the carbon substrate of the cathode is different due to different applied potentials during electrodeposition in a copper salt solution. To ensure the same quality of electrodeposited copper, the same amount of charge is controlled to be transferred. Because the reduction speed of the copper ions is slower at a lower potential, the copper ions can continuously nucleate and grow on the carbon substrate to form larger metal copper particles; under higher potential, the reduction speed of copper ions is higher, so that the metal copper forms core on the carbon substrate instantly, and the tower-shaped copper and the flower-shaped copper with smaller particles are formed.
The invention has the following advantages:
1. the invention adopts an electrochemical system, and the carbon dioxide and the epoxide can be coupled into the five-membered cyclic carbonate at normal temperature and normal pressure, thereby reducing the energy consumption and meeting the standard of green chemistry.
2. The preparation material of the electrocatalyst is easy to obtain, the method is simple, and the electrocatalyst is easy to regulate and control, and is beneficial to large-scale production of the catalyst.
3. The electrocatalyst has smaller grain size and larger specific surface area, thereby containing abundant electrochemical active sites.
Drawings
FIG. 1 is a schematic illustration of an electrochemically deposited copper catalyst according to the present invention; wherein: (a) an electrochemically deposited particulate copper catalyst; (b) an electrochemically deposited, pine-cone shaped copper catalyst; (c) an electrochemically deposited flower-like copper catalyst.
FIG. 2 shows a case where the copper catalyst in the form of particles, a case where the copper catalyst in the form of a pine cone, a case where the copper catalyst in the form of a flower, and a copper flake are at-0.59V RHE The conversion rate of the epoxy styrene and the yield of the carbonic styrene ester are improved after electrochemical reduction for 6 hours under overpotential.
Detailed Description
For a further understanding of the present invention, the following description is given in conjunction with the examples which are set forth to illustrate, but are not to be construed to limit the present invention, features and advantages.
Example 1
Adopting a single electrolytic cell three-electrode system, using carbon paper (1cm x 1.5 cm) as a working electrode, a platinum wire as a counter electrode and Ag/AgCl as a reference electrode, adding 0.1mol/l copper sulfate aqueous solution into an electrolytic cell, and performing electrolytic treatment at-0.99V RHE Depositing copper under the potential, wherein the standard of electrodeposition is transferred with the charge quantity of 50C. The micro-morphology of the electrocatalyst formed after the copper is electrodeposited on the carbon paper is shown in fig. 1 (a), and the electrodeposited copper is in a loose tower shape.
Synthesizing cyclic carbonate in a three-electrode system of an H-type electrolytic cell to prepare a pinecone-shaped copper catalyst in a cathode cell, taking a platinum sheet (3 x 3 cm) as a counter electrode in an anode cell, and taking Ag/AgCl as a reference electrode in the cathode cell. The capacity of the cathode pool is 15ml, the capacity of the anode pool is 30ml, acetonitrile solution dissolved with zinc chloride of 0.045mol/l and tetrabutylammonium bromide of 0.135mol/l is respectively added into the cathode pool and the anode pool of 15ml and 30 ml. Adding 0.04mol/l of epoxy styrene into the cathode pool, and continuously and stably introducing CO 2 at-0.59V RHE Electrochemical reduction is carried out for 6h under overpotential. The test shows that the conversion rate of styrene oxide after the reaction is 51.54%, and the yield of styrene carbonate is 34.437% (as shown in figure 2).
Example 2
Using a single electric motorDissolving Chi San electrode system, using carbon paper (1 × 1.5 cm) as working electrode, platinum wire as counter electrode, ag/AgCl as reference electrode, adding 0.1mol/l copper sulfate aqueous solution into electrolytic cell, and making the solution be at-1.39V RHE Depositing copper under the potential, wherein the standard of electrodeposition is transferred with the charge quantity of 50C. The micro-morphology of the electrocatalyst formed after the copper is electrodeposited on the carbon paper is shown in fig. 1 (b), and the electrodeposited copper is in a flower shape.
A flower-shaped copper catalyst prepared by synthesizing cyclic carbonate in a three-electrode system of an H-shaped electrolytic cell is arranged in a cathode cell, a platinum sheet (3 x 3 cm) is used as a counter electrode in an anode cell, and Ag/AgCl is used as a reference electrode in the cathode cell. The capacity of a cathode pool is 15ml, the capacity of an anode pool is 30ml, and acetonitrile solution dissolved with 0.045mol/l zinc chloride and 0.135mol/l tetrabutylammonium bromide is respectively added into the cathode pool and the anode pool by 15ml and 30 ml. Adding 0.04mol/l of epoxy styrene into the cathode pool, and continuously and stably introducing CO 2 at-0.59V RHE Electrochemical reduction is carried out for 6h under overpotential. The test reaction gave a styrene oxide conversion of 50.46% and a styrene carbonate yield of 26.631% (see fig. 2).
Comparative example 1
Cyclic carbonates were performed in a three-electrode system in an H-cell, with commercial copper sheets purchased as the working electrode (1 x 1.5 cm) in the cathode cell, platinum sheets (3 x 3 cm) as the counter electrode in the anode cell, and Ag/AgCl as the reference electrode in the cathode cell. The capacity of the cathode pool is 15ml, the capacity of the anode pool is 30ml, acetonitrile solution dissolved with zinc chloride of 0.045mol/l and tetrabutylammonium bromide of 0.135mol/l is respectively added into the cathode pool and the anode pool of 15ml and 30 ml. Adding 0.04mol/l of epoxy styrene into the cathode pool, and continuously and stably introducing CO 2 at-0.59V RHE Electrochemical reduction is carried out for 6h under overpotential. The conversion of styrene oxide after the test reaction was 14.64% and the yield of styrene carbonate was 8.90% (see fig. 2).
Comparative example 2
Adopting a single electrolytic cell three-electrode system, using carbon paper (1 x 1.5 cm) as a working electrode, a platinum wire as a counter electrode and Ag/AgCl as a reference electrode, adding 0.1mol/l copper sulfate aqueous solution into an electrolytic cell, and adding the solution at 0.41V RHE Depositing copper under the potential, wherein the standard of electrodeposition is transferred with the charge quantity of 50C. After electrodeposition of copper on carbon paperThe resulting electrocatalyst has a microstructure as shown in FIG. 1 (c), with the electrodeposited copper present in particulate form.
In a three-electrode system of an H-type electrolytic cell, a granular copper catalyst prepared by synthesizing cyclic carbonate is placed in a cathode cell, a platinum sheet (3 x 3 cm) is used as a counter electrode in an anode cell, and Ag/AgCl is used as a reference electrode in a cathode cell. The capacity of a cathode pool is 15ml, the capacity of an anode pool is 30ml, and acetonitrile solution dissolved with 0.045mol/l zinc chloride and 0.135mol/l tetrabutylammonium bromide is respectively added into the cathode pool and the anode pool by 15ml and 30 ml. Adding 0.04mol/l of epoxy styrene into the cathode pool, and continuously and stably introducing CO 2 at-0.59V RHE Electrochemical reduction is carried out for 6h under overpotential. The test shows that the conversion rate of styrene oxide after the reaction is 36.44%, and the yield of styrene carbonate is 13.758% (as shown in figure 2).
The above is a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment, and variations and advantages which can be conceived by those skilled in the art are also included in the present invention without departing from the spirit and scope of the inventive concept.
Claims (4)
1. The application of the copper catalyst with different morphologies loaded on the carbon substrate is characterized in that: the copper catalyst is applied to electrochemical catalytic reaction for coupling electrochemical fixed carbon dioxide and epoxy styrene;
the electrochemical catalytic reaction is carried out in a three-electrode system of an H-shaped electrolytic cell, and epoxystyrene and carbon dioxide are coupled into styrene carbonate; in the three-electrode system, ag/AgCl is used as a reference electrode and is arranged in a cathode pool, a platinum sheet is used as a counter electrode and is arranged in an anode pool, the cathode pool and the anode pool are separated by a proton exchange membrane, and a copper catalyst and epoxy styrene are placed in the cathode pool; electrolyte solution is filled in the cathode pool and the anode pool, and the electrolyte solution comprises the following components: an electrolyte, a cocatalyst and an organic solvent; continuously and stably introducing CO into the cathode pool 2 Carrying out electrochemical reduction under the condition of constant pressure or constant current;
the electrolyte is zinc chloride, and the cocatalyst is tetrabutylammonium bromide;
the concentration of electrolyte zinc chloride in the reaction system is 0.015 to 0.045mol/l, and the concentration of cocatalyst tetrabutylammonium bromide is 0.045 to 0.135mol/l;
the copper catalyst is loaded on a carbon substrate, and the microscopic morphology of the copper catalyst is granular, pinecone-shaped or flower-shaped; the particle size of the granular copper is 1-2 mu m, the particle size of the pitchy copper is 70-90nm, and the particle size of the flower-shaped copper is 40-60nm;
the copper catalyst is prepared by an electrodeposition method, and the preparation method comprises the following steps:
(1) Preparing a copper salt solution with the concentration of 0.05-0.2mol/L as an electrolyte, wherein the copper salt solution is a copper sulfate solution or a copper chloride solution;
(2) Preparing a copper catalyst on a carbon substrate by using a constant-pressure or constant-current method for electrodeposition, wherein the deposition time is 2-20min;
when the constant voltage method is used for electrodeposition, the constant voltage used for preparing the copper nanoparticle catalyst with granular microscopic morphology is 0.4 to 0.1V RHE (ii) a The constant voltage used for preparing the copper catalyst with the microcosmic appearance of the pinecone is-1.0 to-0.7V RHE (ii) a The constant voltage used for preparing the copper catalyst with the microscopic appearance of flower shape is-1.5 to-1.2V RHE 。
2. The use of a carbon substrate supporting copper catalysts of different morphologies according to claim 1, wherein: the carbon substrate is carbon paper, carbon cloth or carbon felt.
3. The use of a carbon substrate supporting copper catalysts of different morphologies according to claim 1, wherein: and (3) performing electrodeposition in a three-electrode system of the single electrolytic cell, wherein the working electrode is a carbon substrate, the counter electrode is a platinum wire, a platinum sheet or a platinum net, and the reference electrode is a silver/silver chloride, hydrogen electrode, calomel electrode or mercury/mercury oxide electrode.
4. The use of a carbon substrate supporting copper catalysts of different morphologies according to claim 1, wherein: in the electrochemical catalytic reaction system, the organic solvent is acetonitrile, DMF or dioxane.
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| CN111647909A (en) * | 2020-07-01 | 2020-09-11 | 中国科学技术大学 | Dendritic copper electrode with hydrophobic surface and preparation method and application thereof |
| CN112481663A (en) * | 2020-12-15 | 2021-03-12 | 中南大学深圳研究院 | Preparation method of copper nanoflower applied to efficient carbon dioxide reduction reaction to generate ethylene |
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| CN111647909A (en) * | 2020-07-01 | 2020-09-11 | 中国科学技术大学 | Dendritic copper electrode with hydrophobic surface and preparation method and application thereof |
| CN112481663A (en) * | 2020-12-15 | 2021-03-12 | 中南大学深圳研究院 | Preparation method of copper nanoflower applied to efficient carbon dioxide reduction reaction to generate ethylene |
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