CN111519206B - Copper-based composite thin film catalyst, and preparation method and application thereof - Google Patents

Copper-based composite thin film catalyst, and preparation method and application thereof Download PDF

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CN111519206B
CN111519206B CN202010402125.2A CN202010402125A CN111519206B CN 111519206 B CN111519206 B CN 111519206B CN 202010402125 A CN202010402125 A CN 202010402125A CN 111519206 B CN111519206 B CN 111519206B
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thin film
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catalyst
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孔祥栋
柯景文
迟明芳
耿志刚
曾杰
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University of Science and Technology of China USTC
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
    • C25B3/20—Processes
    • C25B3/25—Reduction
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention provides a copper-based composite thin film catalyst, which comprises a thin film substrate with micropores, a copper film arranged on the thin film substrate, a cobalt phthalocyanine compound thin film arranged on the copper film and a carbon material layer arranged on the cobalt phthalocyanine compound thin film. Compared with the prior art, the copper-based composite film catalyst has the advantages that the cobalt phthalocyanine compound and the carbon material are introduced on the copper film, so that the copper-based composite film catalyst has hydrophobicity, the current density and the Faraday efficiency of the copper-based composite film catalyst in the reaction of preparing ethylene by electrocatalytic carbon dioxide reduction are improved, and the reaction activity and the selectivity of the catalyst are further improved.

Description

Copper-based composite thin film catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a copper-based composite thin film catalyst, and a preparation method and application thereof.
Background
Excessive combustion of fossil fuels emits large amounts of carbon dioxide, further contributing to energy shortages and environmental crisis. To alleviate the growing energy demands and increasingly fragile environmental conditions, researchers have developed a range of means, such as chemical conversion, photoreduction, biotransformation, and electroreduction, to convert carbon dioxide to useful chemicals and feedstocks. Among these conversion processes, the electroreduction of carbon dioxide, which is carried out at atmospheric pressure and room temperature, is one of the promising methods to promote carbon dioxide utilization and global carbon recycling.
In the electroreduction of carbon dioxide, hithertoVarious carbonaceous products have been reported so far, including carbon monoxide, formate, methane, ethylene, propylene, ethanol, acetate, and the like. Wherein, the polycarbon product (C)2+) Due to its unique molecular structure and high heat of combustion, it has been widely used as a key raw material for industrial manufacturing and liquid fuels. Therefore, the construction of the high-efficiency multi-carbon product electrocatalyst has important significance for the carbon dioxide electroreduction.
Copper-based catalysts are considered to be the most effective catalysts for producing multi-carbon products due to their unique chemical composition and electronic structure. Over the past decade, scientists have developed a variety of efficient copper-based catalysts for the production of multi-carbon products by constructing active phases and assembling composites. Composite catalysts such as copper-zinc bimetallic, copper-silver bimetallic, gold-copper bimetallic, and copper compounds have been developed. However, these catalysts are limited by cumbersome preparation processes and low selectivity to multi-carbon products. Therefore, it is of great significance to explore the copper-based composite catalyst which is low in cost and high in activity.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a copper-based composite thin film catalyst with high selectivity and catalytic activity, and a preparation method and an application thereof.
The invention provides a copper-based composite thin film catalyst, which comprises a thin film substrate with micropores, a copper film arranged on the thin film substrate, a cobalt phthalocyanine compound thin film arranged on the copper film and a carbon material layer arranged on the cobalt phthalocyanine compound thin film.
Preferably, the average diameter of the micropores of the film substrate is 1 to 2 μm.
Preferably, the thickness of the copper film is 400-800 nm.
Preferably, the loading amount of the cobalt phthalocyanine compound in the copper-based composite thin film catalyst is 0.05-0.1 mg/cm2。
Preferably, the loading amount of the carbon material in the copper-based composite thin film catalyst is 0.05-0.2 mg/cm2。
Preferably, the cobalt phthalocyanine compound film is a cobalt phthalocyanine film; the carbon material layer is a carbon black layer.
The invention also provides a preparation method of the copper-based composite film catalyst, which comprises the following steps:
s1) obtaining a film substrate compounded with a copper film on the film substrate with micropores through magnetron sputtering;
s2) spraying a cobalt phthalocyanine compound and a carbon material on the film substrate compounded with the copper film in sequence to obtain the copper-based composite film catalyst.
Preferably, the current of the magnetron sputtering is 40-80 milliamperes; the magnetron sputtering time is 50-80 min.
Preferably, the pressure of argon gas in the magnetron sputtering is 2 x 10-3～3×10-3Millibar.
The invention also provides the application of the copper-based composite film catalyst in electrocatalysis of carbon dioxide reduction reaction.
The invention provides a copper-based composite thin film catalyst, which comprises a thin film substrate with micropores, a copper film arranged on the thin film substrate, a cobalt phthalocyanine compound thin film arranged on the copper film and a carbon material layer arranged on the cobalt phthalocyanine compound thin film. Compared with the prior art, the copper-based composite film catalyst has the advantages that the cobalt phthalocyanine compound and the carbon material are introduced on the copper film, so that the copper-based composite film catalyst has hydrophobicity, the current density and the Faraday efficiency of the copper-based composite film catalyst in the reaction of preparing ethylene by electrocatalytic carbon dioxide reduction are improved, and the reaction activity and the selectivity of the catalyst are further improved.
Drawings
FIG. 1 is a scanning electron microscope photograph of a polytetrafluoroethylene-copper film obtained in example 1 of the invention;
FIG. 2 is a scanning electron microscope photograph of a polytetrafluoroethylene-copper film obtained in example 1 of the invention;
FIG. 3 is a scanning tunneling electron microscope photograph of copper thin film particles of the PTFE-copper thin film obtained in example 1 of the present invention;
fig. 4 is an image of scanning electron elements after the polytetrafluoroethylene-copper film is sprayed with cobalt phthalocyanine in example 2 of the invention;
FIG. 5 is a contact angle test chart of the copper-based composite thin film catalyst obtained in example 2 of the present invention;
FIG. 6 is a scanning electron microscope image of a section of the copper-based composite thin film catalyst obtained in example 2 of the present invention;
FIG. 7 is a graph of the Faraday efficiencies of the microporous hydrophobic Cu/CoPc composite thin film catalyst and the microporous hydrophobic Cu thin film catalyst of example 2 of the present invention for ethylene production at different set currents;
FIG. 8 is a graph of the effective current density of microporous hydrophobic Cu/CoPc composite thin film catalyst and microporous hydrophobic Cu thin film catalyst for ethylene production at different set currents according to example 2 of the present invention;
FIG. 9 is a graph showing the change trend of the faradaic efficiency and overpotential of ethylene in 20 hours of continuous operation of the microporous hydrophobic Cu/CoPc composite thin film catalyst of example 2 of the present invention at a set current of 480 mA/cm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a copper-based composite thin film catalyst, which comprises a thin film substrate with micropores, a copper film arranged on the thin film substrate, a cobalt phthalocyanine compound thin film arranged on the copper film and a carbon material layer arranged on the cobalt phthalocyanine compound thin film.
In the present invention, the thin film substrate having micro-pores provides a copper-based thin film composite with a gas diffusion channel; the average direct optimization of micropores of the film substrate is 1-2 mu m; the non-membrane substrate having micropores is preferably a polytetrafluoroethylene membrane.
A copper film is arranged on the film substrate with the micropores; the thickness of the copper film is preferably 400-800 nm, more preferably 500-700 nm, and still more preferably 600nm.
A cobalt phthalocyanine compound film is arranged on the copper film; the cobalt phthalocyanine compound film is preferably cobalt phthalocyanine; the preferable load capacity of the cobalt phthalocyanine compound in the copper-based composite thin film catalyst is 0.05-0.1 mg/cm2More preferably 0.06-0.09 mg/cm2And more preferably 0.06-0.08 mg/cm2Most preferably 0.075mg/cm2. The invention remarkably improves the activity and selectivity of the reaction for preparing ethylene by electrocatalysis carbon dioxide reduction by compounding the cobalt phthalocyanine compound with the capability of preparing carbon monoxide by electrocatalysis carbon dioxide reduction.
A carbon material layer is arranged on the cobalt phthalocyanine compound film; the carbon material layer is preferably a carbon black layer; the preferable load capacity of the carbon material in the copper-based composite thin film catalyst is 0.05-0.2 mg/cm2More preferably 0.08 to 0.16mg/cm2More preferably 0.1 to 0.14mg/cm2Most preferably 0.1 to 0.12mg/cm2。
According to the invention, the cobalt phthalocyanine compound and the carbon material are introduced on the copper film, so that the copper-based composite film catalyst has hydrophobicity, the current density and Faraday efficiency of the copper-based composite film catalyst in the reaction of preparing ethylene by electrocatalytic carbon dioxide reduction are improved, and the reaction activity and selectivity of the catalyst are further improved.
The invention also provides a preparation method of the copper-based composite thin film catalyst, which comprises the following steps: s1) obtaining a film substrate compounded with a copper film on the film substrate with micropores through magnetron sputtering; s2) spraying a cobalt phthalocyanine compound and a carbon material on the film substrate compounded with the copper film in sequence to obtain the copper-based composite film catalyst.
Wherein, the film substrate with micropores is the same as the above, and is not described in detail herein.
Obtaining a film substrate compounded with a copper film on a film substrate with micropores through magnetron sputtering; the invention specifically comprises the following steps: taking a film with micropores as a substrate, taking a copper disc as a target material, and carrying out magnetron sputtering on a copper film under the action of argon ions of a sputtering source to obtain a film substrate compounded with the copper film; the above-mentionedThe current of magnetron sputtering is preferably 40-80 milliamperes, more preferably 50-70 milliamperes, and further preferably 60 milliamperes; the magnetron sputtering time is preferably 50-80 min, and more preferably 60-70 min; the pressure of argon gas during magnetron sputtering is preferably 2X 10-3～3×10-3Mbar, more preferably 2.2X 10-3～2.8×10-3Mbar, more preferably 2.4X 10-3～2.6×10-3Mbar; the flow rate of argon during magnetron sputtering is preferably 20-100 ml/min.
And sequentially spraying a cobalt phthalocyanine compound and a carbon material on the film substrate compounded with the copper film to obtain the copper-based composite film catalyst. The cobalt phthalocyanine compound and the carbon material are the same as described above, and are not described herein again.
The copper-based composite film catalyst provided by the invention is simple in preparation method, easy to synthesize in large quantities and low in cost.
The invention also provides an application of the copper-based composite film catalyst in electrocatalysis of carbon dioxide reduction reaction; the electrocatalytic carbon dioxide reduction reaction is preferably a reaction for preparing ethylene by electrocatalytic carbon dioxide reduction.
The copper-based composite film catalyst provided by the invention can be used for efficiently electrochemically reducing carbon dioxide into ethylene in a gas diffusion electrolytic cell.
In order to further illustrate the present invention, the following describes a copper-based composite thin film catalyst, a preparation method and applications thereof in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
Fixing the copper disc at a target position, cutting a porous polytetrafluoroethylene film with a size (diameter of 9 cm) suitable for the rotary disc, and sticking the back of the porous polytetrafluoroethylene film to the rotary disc by using a double-sided adhesive tape. And (3) turning on a magnetron sputtering power supply, sequentially arranging a mechanical pump and a molecular pump, and firstly setting the highest power of the molecular pump. After about half an hour the system reaches the appropriate vacuum value (5X 10)-6Millibar). Reducing 40 percent of the highest power of the rotating speed value of the molecular pump, opening an argon switch, and regulating the argon flow to be 100 ml-And (3) minutes. The dc power supply is turned on and a constant current mode is set, wherein the current is set to 100 milliamps. After the target copper disk is observed to be glowed from the glass window, the rotating speed of the molecular pump is sequentially increased to 70% of the maximum power, the current is reduced to 40 milliamperes, and the flow rate of argon is reduced to 20 milliliters per minute. And starting timing, setting the current to be 0 after 1 hour, and closing the magnetron sputtering device to obtain the polytetrafluoroethylene-copper film.
The teflon-copper thin film obtained in example 1 was analyzed by a scanning electron microscope, and scanning electron microscope pictures thereof were shown in fig. 1 and 2.
Scanning tunneling electron microscopy and electron diffraction were performed on the copper film particles, as shown in FIG. 3.
Example 2
0.1mg/cm of carbon black was directly sprayed on the polytetrafluoroethylene-copper film obtained in example 1 to obtain a microporous hydrophobic Cu film catalyst.
The teflon-copper film obtained in example 1 was first sprayed with 0.075mg/cm cobalt phthalocyanine, and after the teflon-copper film was sprayed with cobalt phthalocyanine, scanning electron element imaging was performed, yielding fig. 4. And spraying 0.1 mg/square centimeter of carbon black to obtain the microporous hydrophobic Cu/CoPc composite film catalyst, namely the copper-based composite film catalyst.
The contact angle of the microporous hydrophobic Cu/CoPc composite thin film catalyst obtained in example 2, i.e., the copper-based composite thin film catalyst, was measured, and the results are shown in fig. 5.
The microporous hydrophobic Cu/CoPc composite thin film catalyst obtained in example 2, i.e., the copper-based composite thin film catalyst, was subjected to slice electron microscopy imaging to obtain a slice scanning electron microscope image shown in FIG. 6.
Example 3
The electrocatalytic carbon dioxide reduction test conditions of the microporous hydrophobic Cu/CoPc composite thin film catalyst, namely the copper-based composite thin film catalyst obtained in example 2, are as follows:
in the flow cell system, a Nafion 115 membrane is used as an ion exchange membrane, and a microporous hydrophobic Cu/CoPc composite thin film catalyst, namely the copper-based composite thin film catalyst, a graphite electrode and a silver/silver chloride electrode obtained in example 2, are used as a working electrode, a counter electrode and a reference electrode, respectively. The catalytic reaction selected 1 mol/l potassium hydroxide as an electrolyte, and the electrolyte was flowed at a rate of 5 ml/min using a peristaltic pump, and a flow rate of carbon dioxide was set to 10 ml/min.
Example 4
And (3) testing the product selectivity of the microporous hydrophobic Cu/CoPc composite thin film catalyst in the electrocatalytic carbon dioxide reduction.
Under the reaction conditions of example 3, a galvanostatic test was employed. The total current was set at 60 milliamps/square centimeter and the galvanostatic test was run for 1 hour. During the reaction, the carbon dioxide flow rate was set at 10 ml/min. Oxygen generated by the anode during the reaction is discharged into the air. The ethylene content in the catalytic product was monitored on-line using gas chromatography. After the test was completed, the total current was set to 120, 180, 240, 300, 360, 420, and 480 milliamps/square centimeter in this order, and the test was performed while the other conditions were maintained. The faradaic efficiency of the obtained microporous hydrophobic Cu/CoPc composite thin film catalyst in electrocatalysis and the faradaic efficiency of the microporous hydrophobic Cu thin film catalyst in electrocatalysis to generate ethylene is shown in figure 7, and the current density of ethylene part is shown in figure 8.
Example 5
The total current is set to be 480/square centimeter for electrolysis, and the catalytic stability of the microporous hydrophobic Cu/CoPc composite thin film catalyst, namely the copper-based composite thin film catalyst obtained in the example 2, in the preparation of ethylene by electrocatalysis of carbon dioxide reduction is tested.
Under the reaction conditions of example 3 and example 4, a galvanostatic test was taken. The total current was set to 480/cm and electrolysis was carried out at constant current for 20 hours. And monitoring the potential of the working electrode in real time in the electrolytic process, and monitoring the content of ethylene in the catalytic product on line by using gas chromatography. The change trend of the electrolytic potential and the ethylene selectivity of the microporous hydrophobic Cu/CoPc composite thin film catalyst with time is shown in figure 9.

Claims (7)

1. A copper-based composite thin film catalyst is characterized by comprising a thin film substrate with micropores, a copper film arranged on the thin film substrate, a cobalt phthalocyanine compound thin film arranged on the copper film and a carbon material layer arranged on the cobalt phthalocyanine compound thin film;
the load capacity of the cobalt phthalocyanine compound in the copper-based composite thin film catalyst is 0.05-0.1 mg/cm2；
The loading amount of the carbon material in the copper-based composite thin film catalyst is 0.05-0.2 mg/cm2；
The average diameter of the micropores of the film substrate is 1-2 μm.
2. The copper-based composite thin film catalyst according to claim 1, wherein the thickness of the copper film is 400 to 800 nm.
3. The copper-based composite thin film catalyst according to claim 1, wherein the cobalt phthalocyanine-based compound thin film is a cobalt phthalocyanine thin film; the carbon material layer is a carbon black layer.
4. The preparation method of the copper-based composite thin film catalyst according to claim 1, comprising:
s1) obtaining a film substrate compounded with a copper film on the film substrate with micropores through magnetron sputtering;
s2) spraying a cobalt phthalocyanine compound and a carbon material on the film substrate compounded with the copper film in sequence to obtain the copper-based composite film catalyst.
5. The preparation method according to claim 4, wherein the magnetron sputtering current is 40-80 mA; the magnetron sputtering time is 50-80 min.
6. The method according to claim 4, wherein the pressure of argon gas in magnetron sputtering is 2 x 10-3~3×10-3Millibar.
7. The use of the copper-based composite thin film catalyst of claim 1 in electrocatalytic carbon dioxide reduction reactions.
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