CN114395769A - Supported copper catalyst and preparation method and application thereof - Google Patents

Supported copper catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114395769A
CN114395769A CN202210111273.8A CN202210111273A CN114395769A CN 114395769 A CN114395769 A CN 114395769A CN 202210111273 A CN202210111273 A CN 202210111273A CN 114395769 A CN114395769 A CN 114395769A
Authority
CN
China
Prior art keywords
copper
catalyst
cerium
supported copper
supported
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210111273.8A
Other languages
Chinese (zh)
Other versions
CN114395769B (en
Inventor
熊宇杰
江亚文
李嘉威
龙冉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202210111273.8A priority Critical patent/CN114395769B/en
Publication of CN114395769A publication Critical patent/CN114395769A/en
Application granted granted Critical
Publication of CN114395769B publication Critical patent/CN114395769B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C25B11/055—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
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • 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
    • 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 provides a supported copper catalyst, wherein a carrier of the supported copper catalyst is cerium oxide quantum dots, and an active substance is a copper monoatomic atom. The invention provides a preparation method of a supported copper catalyst, which comprises the steps of using polyhydric alcohol as a solvent, a stabilizer and a reducing agent, heating to synthesize cerium oxide quantum dots, cooling reaction liquid, adding a copper source, and heating to obtain the cerium oxide quantum dot supported copper monatomic catalyst. The preparation method of the supported copper catalyst provided by the invention is simple to operate and easy to amplify, and very high methane selectivity and methane partial current density are obtained when a flow cell is used for carrying out electrocatalytic carbon dioxide reduction reaction. The invention also provides an application of the supported copper catalyst.

Description

Supported copper catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a supported copper catalyst, a preparation method and an application thereof, in particular to a supported copper electrocatalyst, a preparation method thereof and a method for preparing methane by electrocatalysis reduction of carbon dioxide by adopting the catalyst.
Background
Fossil energy is a main energy source for the development of the society and the production and life of human beings at present. Carbon dioxide is discharged into the atmosphere as a final product in the use process of fossil energy, and excessive carbon dioxide discharge can cause a plurality of environmental problems such as seawater acidification, greenhouse effect and the like, thereby bringing great threat to the sustainable development of the human society.
The conversion of carbon dioxide and water into valuable products such as carbon monoxide, methane, ethylene and the like by an electrocatalytic method is considered to be a very promising carbon dioxide conversion utilization mode. The carbon monoxide and the formate can be prepared by two-electron transfer reduction and other methods by using various catalysts, and high selectivity (the Faraday efficiency is more than 95 percent) and high current density (more than 100 mA/cm) are realized at present2) And long-term stability (greater than 100 h). Methane is a very valuable carbon dioxide electroreduction product which can be directly used in a very mature natural gas industrial system, but carbon dioxide needs 8 electrons to be reduced to generate methane, and the preparation of methane with high selectivity and high current density is still a challenge at present.
Disclosure of Invention
In view of the above, the present invention provides a supported copper catalyst, a preparation method and an application thereof, and the supported copper catalyst provided by the present invention exhibits high methane selectivity and current density of methane fraction in electrocatalytic carbon dioxide reduction.
The invention provides a supported copper catalyst, which comprises:
the carrier is cerium oxide quantum dots;
an active material, the active material being a copper atom.
Preferably, the molar ratio of copper to cerium in the supported copper catalyst is (1-20): 100.
preferably, the size of the cerium oxide quantum dot is 1-10 nm.
Preferably, the copper atoms are distributed in a monoatomic state on the surface of the cerium oxide quantum dot.
The invention provides a preparation method of the supported copper catalyst in the technical scheme, which comprises the following steps:
and mixing the copper source and the cerium source solution and then reacting to obtain the supported copper catalyst.
Preferably, the copper source is selected from one or more of copper nitrate trihydrate, copper acetate, copper sulfate and copper acetylacetonate.
Preferably, the preparation method of the cerium source solution comprises:
mixing a cerium source and a solvent, and reacting to obtain a cerium source solution.
Preferably, the cerium source is selected from one or more of cerium nitrate hexahydrate, cerium acetate and cerium acetylacetonate;
the solvent is selected from polyols.
Preferably, the mixing temperature is 60-120 ℃;
the reaction temperature is 160-220 ℃.
The invention provides an application of the supported copper catalyst in the technical scheme in preparation of methane.
The copper-based catalyst is the most widely researched electrocatalyst for synthesizing more than two electron transfer reduction products at present, but in the invention, the electrocatalytic carbon dioxide reduction reaction mechanism is complex, and various steps such as C-O bond breakage, C-H bond and C-C bond generation and the generation paths of various products are involved, and meanwhile, the competition of hydrogen evolution side reaction is also faced, so that the reasonable design of the copper-based catalyst is the key for electrocatalytic conversion of methane with high activity and high selectivity. The invention uses polyalcohol as solvent, stabilizer and reducer to synthesize cerium oxide (CeO) by a two-step heating method2) The invention relates to a quantum dot supported copper monatomic catalyst, and cerium oxide quantum dot catalysts with different copper loading amounts can be prepared by adjusting the addition amount of a copper source.
The invention provides a supported copper catalyst, which comprises a cerium oxide quantum dot carrier and a copper monatomic active site. The catalyst provided by the invention takes low-cost polyalcohol as a solvent, a stabilizer and a reducing agent, and the cerium oxide quantum dot loaded copper catalyst is obtained by a simple two-step heating method. The preparation method of the catalyst provided by the invention has the advantages of low price of used raw materials, simple operation and easy amplification.
In the catalyst provided by the invention, the cerium oxide quantum dots serving as the carrier are less than 10nm, have large specific surface area and simultaneously have large specific surface areaThe surface has a plurality of oxygen defects, so that high load of copper on the surface can be realized, the copper is distributed in a single-atom state on the surface of the cerium oxide quantum dot, and the active sites of the copper are isolated, so that the carbon-carbon coupling step is not easy to occur in the electrocatalytic carbon dioxide reduction process, and the generation of byproducts of ethylene, ethanol and propanol is reduced; the copper monatomic active site also has stronger adsorption capacity on a carbon monoxide intermediate in the electrocatalysis carbon dioxide reduction process, so that the deep hydrogenation of the carbon monoxide intermediate is easy, and the high methane product selectivity is finally shown; at 200mA/cm2～600mA/cm2When the current is constant, the Faraday efficiency of methane can exceed 60 percent, the highest Faraday efficiency of methane can be 67 percent, and the current density of the highest methane part is 364mA/cm2And shows good potential for industrial application.
Drawings
FIG. 1 is an atomic resolution transmission electron microscope image of a cerium oxide quantum dot supported copper catalyst with a molar ratio of copper to cerium of 10% prepared in example 4 of the present invention;
FIG. 2 is an XRD diffraction pattern of cerium oxide quantum dot supported copper catalysts with different copper to cerium molar ratios prepared in examples 1-4 of the present invention;
FIG. 3 is a synchrotron radiation characterization of cerium oxide quantum dot supported copper catalysts of different copper to cerium molar ratios prepared in examples 1-4 of the present invention;
FIG. 4 is a line graph of Faraday efficiency of methane produced by electrocatalytic carbon dioxide reduction of cerium oxide quantum dot-supported copper catalysts with different copper-to-cerium molar ratios, prepared in examples 5 to 8 of the present invention;
fig. 5 is a plot of the current density of methane part corresponding to electrocatalytic carbon dioxide reduction by a constant current method for cerium oxide quantum dot-supported copper catalysts with different copper-to-cerium molar ratios prepared in examples 5-8 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 supported copper catalyst, which comprises:
the carrier is cerium oxide quantum dots;
an active material, the active material being a copper atom.
In the present invention, the active substance is supported on a carrier.
In the invention, the size of the cerium oxide quantum dot is preferably 1-10 nm, more preferably 2-8 nm, more preferably 2-6 nm, and most preferably 2-3 nm.
In the present invention, the copper atoms are preferably copper monoatomic atoms, and the copper atoms are preferably distributed in a monoatomic state on the surface of the cerium oxide quantum dots.
In the invention, the molar ratio of copper to cerium in the supported copper catalyst is preferably (1-20): 100, more preferably (5-15) 100, and still more preferably (8-12): 100, most preferably 10: 100.
the invention provides a preparation method of the supported copper catalyst in the technical scheme, which comprises the following steps:
and mixing the copper source and the cerium source solution and then reacting to obtain the supported copper catalyst.
In the present invention, the copper source is preferably selected from one or more of copper nitrate trihydrate, copper acetate, copper sulfate and copper acetylacetonate.
In the present invention, the preparation method of the cerium source solution preferably includes:
mixing a cerium source and a solvent, and reacting to obtain a cerium source solution.
In the present invention, the cerium source is preferably one or more selected from cerium nitrate hexahydrate, cerium acetate and cerium acetylacetonate.
In the present invention, the solvent is preferably selected from polyhydric alcohols, and more preferably selected from one or more of triethylene glycol, diethylene glycol, and ethylene glycol.
In the invention, the ratio of the cerium source to the solvent is preferably (100-2000) mg: (25-100) mL, more preferably (500-1500) mg: (30-90) mL, more preferably (800-1200) mg: (40-80) mL, most preferably 1000 mg: (50-70) mL.
In the present invention, the mixing of the cerium source and the solvent is referred to as a first mixing, which is preferably performed under stirring; the temperature of the first mixing is preferably 60-120 ℃, more preferably 70-110 ℃, more preferably 80-100 ℃, and most preferably 100 ℃; the time for the first mixing is preferably 10 to 60min, more preferably 20 to 50min, and most preferably 30 to 40 min.
In the present invention, the reaction performed after the first mixing is referred to as a first reaction, and the first reaction is preferably performed under stirring; the temperature of the first reaction is preferably 160-220 ℃, more preferably 170-210 ℃, more preferably 180-200 ℃ and most preferably 180 ℃; the time of the first reaction is preferably 10 to 120min, more preferably 30 to 100min, more preferably 50 to 80min, and most preferably 60 to 70 min.
In the present invention, it is preferable that the heating is stopped after the first reaction is completed, and the obtained reaction solution is cooled to room temperature to obtain a cerium source solution.
In the invention, the mole ratio of copper in the copper source and cerium in the cerium source solution is preferably (1-20): 100, more preferably (5-15) 100, and still more preferably (8-12): 100, most preferably 10: 100.
in the invention, the mixing of the copper source and the cerium source solution is recorded as a second mixing; the second mixing is preferably carried out under stirring; the second mixing temperature is preferably 60-120 ℃, more preferably 70-110 ℃, more preferably 80-100 ℃, and most preferably 100 ℃; the second mixing time is preferably 10 to 60min, more preferably 20 to 50min, and most preferably 30 to 40 min.
In the present invention, the reaction after the second mixing is referred to as a second reaction; the second reaction is preferably carried out under stirring; the temperature of the second reaction is preferably 160-220 ℃, more preferably 170-210 ℃, more preferably 180-200 ℃ and most preferably 180 ℃; the time of the second reaction is preferably 10 to 120min, more preferably 30 to 100min, more preferably 50 to 80min, and most preferably 60 to 70 min.
In the present invention, it is preferable that the second reaction further comprises, after completion of the first reaction:
the heating was stopped, and the obtained reaction solution was cooled to room temperature.
In the present invention, it is preferable that the second reaction further comprises, after completion of the first reaction:
and precipitating, washing and drying the obtained reaction product to obtain the supported copper catalyst.
In the present invention, the reagent of the precipitant is preferably a mixed solvent, and more preferably includes: strongly polar solvents and weakly polar solvents.
In the present invention, the strongly polar solvent is preferably selected from one or more of methanol, ethanol and isopropanol; the weak polar solvent is preferably selected from one or more of ethyl acetate, n-hexane and cyclohexane; the volume ratio of the strong polar solvent to the weak polar solvent is preferably (0.1-1): 1, more preferably (0.3 to 0.7): 1, more preferably (0.4 to 0.6): 1, most preferably 0.5: 1.
the invention provides an application of the supported copper catalyst in the technical scheme in preparation of methane.
In the present invention, the method for producing methane is preferably electrocatalytic reduction of carbon dioxide to methane.
In the present invention, the method for producing methane more preferably comprises:
preparing methane by electrocatalysis of carbon dioxide reduction by adopting a three-electrode chemical system and a constant current potential or constant current method;
the working electrode in the three-electrode chemical system is prepared from the supported copper catalyst in the technical scheme.
In the present invention, the working electrode is preferably assembled into an electrocatalytic carbon dioxide reduction flow cell during the electrocatalytic carbon dioxide reduction process for producing methane.
In the present invention, the method for preparing the working electrode preferably includes:
coating the catalyst ink on the surface of the gas diffusion electrode and then drying to obtain a working electrode;
the catalyst ink contains the supported copper type catalyst in the technical scheme.
In the present invention, the method for preparing the catalyst ink preferably includes:
and mixing the supported copper catalyst and the Nafion solution in the dispersion liquid to obtain the catalyst ink.
In the invention, the mass concentration of the Nafion solution is preferably 0.1-10%, more preferably 0.5-8%, more preferably 1-6%, more preferably 2-5%, and most preferably 3-4%.
In the present invention, the dispersion is preferably selected from low boiling point solvents, more preferably from one or more of methanol, ethanol, propanol and isopropanol.
In the invention, the volume ratio of the Nafion solution to the dispersion liquid is preferably (0.001-1): 1, more preferably (0.005 to 0.8): 1, more preferably (0.01 to 0.6): 1, more preferably (0.05 to 0.4): 1, more preferably (0.1 to 0.3): 1, most preferably 0.2: 1.
in the invention, the concentration of the supported copper catalyst in the catalyst ink is preferably 1-10 mg/mL, more preferably 2-8 mg/mL, more preferably 3-6 mg/mL, and most preferably 4-5 mg/mL.
In the invention, the mixing method is preferably ultrasonic, so that the supported copper type catalyst is uniformly dispersed.
In the present invention, the gas diffusion electrode is preferably selected from a carbon-based material gas diffusion electrode or a PTFE gas diffusion electrode.
In the invention, the loading capacity of the copper-loaded catalyst in the catalyst ink on the gas diffusion electrode is preferably 0.05-5 mg/cm2More preferably 0.1 to 3mg/cm2More preferably 0.5 to 2mg/cm2Most preferably 0.7mg/cm2。
In the present invention, the three-electrode electrochemical system preferably further comprises:
a reference electrode, a counter electrode and an electrolyte.
In the present invention, the reference electrode is preferably selected from one or more of a silver/silver chloride electrode, a calomel electrode, and a mercury-mercury oxide electrode; the counter electrode is preferably selected from one or more of a nickel mesh electrode, a platinum carbon electrode, a glassy carbon electrode and a carbon rod electrode; the electrolyte is preferably selected from KOH solution, NaOH solution, KHCO3Solution, NaHCO3Solution, K2CO3Solution, Na2CO3Solution, KCl solution, NaCl solution, K2SO4Solution and Na2SO4One or more of the solutions.
In the invention, the flow rate of the carbon dioxide gas in the methane preparation process is preferably 1-200 sccm, more preferably 10-150 sccm, more preferably 50-120 sccm, and most preferably 80-100 sccm; the flow rates of the catholyte and the anolyte are preferably selected from 0.1-100 mL/min, more preferably 0.5-80 mL/min, more preferably 1-60 mL/min, more preferably 10-50 mL/min, more preferably 20-40 mL/min, and most preferably 30mL/min independently.
In the present invention, the potential during the potentiostatic method is preferably-0.1 to-2V, more preferably-0.5 to-1.5V, most preferably-1V; the current density in the constant current method process is preferably 1-1000 mA/cm2More preferably 10 to 800mA/cm2More preferably 50 to 600mA/cm2More preferably 100 to 400mA/cm2Most preferably 200 to 300mA/cm2。
The invention provides a supported copper catalyst, which comprises a cerium oxide quantum dot carrier and a copper monatomic active site. The preparation method of the copper catalyst provided by the invention has the advantages of low price of used raw materials, simple operation and easy amplification. The carrier cerium oxide quantum dot is less than 10nm, has a large specific surface area, has a plurality of oxygen defects on the surface, can realize high load of copper on the surface of the cerium oxide quantum dot, and the copper is distributed on the surface of the cerium oxide quantum dot in a single atom state; the copper monatomic active site also has stronger adsorption capacity on a carbon monoxide intermediate in the electrocatalysis carbon dioxide reduction process, so that the deep hydrogenation of the carbon monoxide intermediate is easy, and finally, the catalyst shows high methane product selectivity.
Example 1
Accurately weighing 868.4mg of cerous nitrate hexahydrate, adding the cerous nitrate hexahydrate into 50mL of triethylene glycol, heating the solution to 100 ℃ under magnetic stirring, and maintaining stirring for 30min to completely dissolve the cerous nitrate hexahydrate to obtain a reaction solution;
heating the reaction solution from 100 ℃ to 180 ℃, and maintaining the temperature of 180 ℃ for heating for 30min under the magnetic stirring state; then, stopping heating and stirring, and naturally cooling the reaction liquid to room temperature to obtain a reaction product;
washing the reaction product with a mixed solvent of ethanol and ethyl acetate (volume ratio of 1:7), centrifuging, and drying in a vacuum drying oven at 60 deg.C overnight to obtain cerium oxide quantum dot catalyst marked as CeO2QD。
Example 2
Accurately weighing 868.4mg of cerous nitrate hexahydrate, adding the cerous nitrate hexahydrate into 50mL of triethylene glycol, heating the solution to 100 ℃ under magnetic stirring, and maintaining stirring for 30min to completely dissolve the cerous nitrate hexahydrate to obtain a reaction solution;
heating the reaction solution from 100 ℃ to 180 ℃, and maintaining the temperature of 180 ℃ for heating for 30min under the magnetic stirring state; then stopping heating and stirring, and naturally cooling the reaction solution to room temperature to obtain a cooled reaction solution;
adding 9.7mg of copper nitrate trihydrate into the cooled reaction liquid, heating the solution to 100 ℃ under magnetic stirring, and maintaining stirring for 30min to completely dissolve the copper nitrate trihydrate to obtain a mixed solution;
heating the mixed solution from 100 ℃ to 180 ℃, and maintaining the temperature of 180 ℃ for heating for 30min under the magnetic stirring state; then, stopping heating and stirring, and naturally cooling the reaction liquid to room temperature to obtain a reaction product;
washing the product with a mixed solvent of ethanol and ethyl acetate (volume ratio of 1:7), centrifuging, drying in a vacuum drying oven at 60 ℃ overnight to obtain a cerium oxide quantum dot-supported copper catalyst with a molar ratio of copper to cerium of 2%, wherein the cerium oxide quantum dot-supported copper catalyst is marked as CeO2QD-2％Cu。
Example 3
A cerium oxide quantum dot supported copper catalyst was prepared according to the method of example 2, differing from example 2 in that 33.8mg of copper nitrate trihydrate was added to prepare a cerium oxide quantum dot supported copper catalyst having a copper to cerium molar ratio of 7%, labeled as CeO2QD-7％Cu。
Example 4
A cerium oxide quantum dot supported copper catalyst was prepared according to the method of example 2, differing from example 2 in that 48.3mg by mass of copper nitrate trihydrate was added to prepare a cerium oxide quantum dot supported copper catalyst having a copper to cerium molar ratio of 10%, labeled as CeO2QD-10％Cu。
FIG. 1 shows CeO obtained in example 42Transmission electron microscope pictures of QD-10% Cu show that the prepared CeO2The quantum dot size is around 2nm, and since the atomic number of Cu is lower than that of Ce, Cu atoms cannot be observed from the spherical aberration electron microscope image.
FIG. 2 shows CeO prepared in examples 1 to 42QD，CeO2QD-2％Cu，CeO2QD-7% Cu and CeO2The XRD diffraction patterns of QD-10% Cu revealed that the XRD diffraction patterns of these four catalysts all correspond to those of CeO of fluorite structure2Standard card, no diffraction peaks were observed for copper, cuprous oxide and cupric oxide, indicating that Cu is in CeO2The surface of the quantum dot is in a highly dispersed state.
FIG. 3 is a synchrotron radiation characterization of cerium oxide quantum dot supported copper catalysts with different copper to cerium molar ratios, and the results show that CeO2QD-2％Cu，CeO2QD-7% Cu and CeO2QD-10% Cu onlyCu-O bonds were present, and no Cu-Cu bonds were observed, indicating that Cu was in CeO2The surface of the quantum dot presents a distribution of monoatomic states.
Example 5
The method for generating methane by electrocatalysis of carbon dioxide through using cerium oxide quantum dot loaded copper catalyst, and comprises the following steps:
adding 8mg of the cerium oxide quantum dot supported copper catalyst prepared in example 2 into 1.97mL of isopropanol solution, adding 30uL (microliter) of 5 wt% Nafion solution, and then ultrasonically mixing for 30min to obtain a uniform catalyst mixed solution;
200uL (microliter) of the above catalyst mixed solution was dropped onto a 1.5cm x 1.5cm gas diffusion electrode, and dried under an infrared lamp to obtain a working electrode having a catalyst loading of 0.36mg/cm2；
Separating a cathode tank and an anode tank of the carbon dioxide reduction flow cell by using an anion exchange membrane, assembling the electrocatalytic carbon dioxide reduction flow cell by using a silver/silver chloride electrode as a reference electrode and a foamed nickel as a counter electrode and using the prepared gas diffusion electrode coated with the cerium oxide quantum dot-loaded copper catalyst as a working electrode, wherein the active area of the working electrode is 1cm2；
Using a KOH solution of 1.0M (mol/L) as an electrolyte of a cathode tank and an anode tank, and continuously allowing the electrolyte to flow at a flow rate of 10mL/min by using a peristaltic pump; high-purity carbon dioxide is continuously introduced into the back of the gas diffusion electrode of the cathode slot at the flow rate of 50 sccm; electrocatalytic carbon dioxide reduction reactions were performed using a constant current method with constant currents set at 50mA, 100mA, 200mA, 300mA, 400mA, 500mA, and 600mA, respectively.
Example 6
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 1 was used instead of the catalyst prepared in example 2.
Example 7
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 3 was used instead of the catalyst prepared in example 2.
Example 8
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 4 was used instead of the catalyst prepared in example 2.
Performance detection
Detecting a gas phase product of the electrocatalytic carbon dioxide reduction product by using a gas chromatograph, and detecting a liquid phase product by using a nuclear magnetic resonance spectrometer; according to the amount of the product obtained by determination, calculating according to Faraday's law to obtain the Faraday efficiency of the methane product and the current density of the methane part; the Faraday efficiencies and the methane partial current densities in the methane preparation processes of examples 5-8 were measured, and the measurement results are shown in FIG. 4 and FIG. 5.
FIG. 4 is a line graph of Faraday efficiency of a series of electrocatalytic carbon dioxide reduction methane preparation catalysts prepared in examples 1-4, wherein the electrocatalytic carbon dioxide reduction catalysts have different copper-to-cerium molar ratios; it can be seen that the pure cerium oxide quantum dots (CeO)2QD) produces little methane; when the molar ratio of copper to cerium is 2% (CeO)2QD-2% Cu), the Faraday efficiency of methane is obviously improved to 100-400 mA/cm2Under operation, the Faraday efficiency of methane can reach more than 40%; when the loading continued to increase to a copper to cerium molar ratio of 7% (CeO)2QD-7% Cu), the Faraday efficiency of methane is further improved at 400mA/cm2When the device is operated, the Faraday efficiency of methane can reach 67%; then the loading of copper is increased until the molar ratio of copper to cerium is 10% (CeO)2QD-10% Cu), the faraday efficiency of methane is not further improved, performance and CeO2QD-7% Cu; but at 600mA/cm2In operation, CeO2QD-10% Cu can still maintain the methane Faraday efficiency of more than 60%, and the current density of the corresponding methane part can reach 364mA/cm2(FIG. 5), surpassing most reported copper-based catalysts.
Example 9
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 3 was used instead of the catalyst prepared in example 2.
The Faraday efficiency detection is carried out according to the method of the technical scheme, and the detection result is that 200mA/cm is adopted in the process of preparing methane in the embodiment 92The long-time operation is about 3 hours, and the methane Faraday efficiency of about 60 percent can be maintained in the long-time electrolysis process.
Example 10
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 4 was used in place of the catalyst prepared in example 2, and the loading of the catalyst on the gas diffusion electrode was 0.18mg/cm2。
The Faraday efficiency detection is carried out according to the method of the technical scheme, and the detection result is that in the process of preparing methane in the embodiment 10, the concentration of the carbon dioxide is 300mA/cm2The faradaic efficiency of methane at constant current reaction was 57.3%.
Example 11
Methane was prepared according to the method of example 5, differing from example 5 in that the catalyst prepared in example 4 was used instead of the catalyst prepared in example 2, and the loading of the catalyst on the gas diffusion electrode was 1mg/cm2。
The Faraday efficiency detection is carried out according to the method of the technical scheme, and the detection result is that in the process of preparing methane in the embodiment 11, the concentration of the carbon dioxide is 300mA/cm2The Faraday efficiency of methane is 50.1 percent during constant current reaction
The invention provides a supported copper catalyst, which comprises a cerium oxide quantum dot carrier and a copper monatomic active site. The preparation method of the copper catalyst provided by the invention has the advantages of low price of used raw materials, simple operation and easy amplification. The carrier cerium oxide quantum dot is less than 10nm, has a large specific surface area, has a plurality of oxygen defects on the surface, can realize high load of copper on the surface of the cerium oxide quantum dot, and the copper is distributed on the surface of the cerium oxide quantum dot in a single atom state; the copper monatomic active site also has stronger adsorption capacity on a carbon monoxide intermediate in the electrocatalysis carbon dioxide reduction process, so that the deep hydrogenation of the carbon monoxide intermediate is easy, and finally, the catalyst shows high methane product selectivity.
The foregoing description of the embodiments is provided merely as an aid in understanding the principles and methods of the invention, and it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the principles and scope of the invention as defined in the appended claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A supported copper catalyst comprising:
the carrier is cerium oxide quantum dots;
an active material, the active material being a copper atom.
2. The supported copper catalyst of claim 1, wherein the molar ratio of copper to cerium in the supported copper catalyst is (1-20): 100.
3. the supported copper catalyst of claim 1, wherein the size of the cerium oxide quantum dots is 1 to 10 nm.
4. The supported copper catalyst of claim 1, wherein the copper atoms are distributed in a monoatomic state on the surface of the cerium oxide quantum dots.
5. A method of preparing the supported copper catalyst of claim 1, comprising:
and mixing the copper source and the cerium source solution and then reacting to obtain the supported copper catalyst.
6. The method of claim 5, wherein the copper source is selected from one or more of copper nitrate trihydrate, copper acetate, copper sulfate and copper acetylacetonate.
7. The method of claim 5, wherein the cerium source solution is prepared by a method comprising:
mixing a cerium source and a solvent, and reacting to obtain a cerium source solution.
8. The method according to claim 7, wherein the cerium source is selected from one or more of cerium nitrate hexahydrate, cerium acetate and cerium acetylacetonate;
the solvent is selected from polyols.
9. The method according to claim 5, wherein the temperature of the mixing is 60-120 ℃;
the reaction temperature is 160-220 ℃.
10. Use of the supported copper catalyst of claim 1 in the preparation of methane.
CN202210111273.8A 2022-01-29 2022-01-29 Supported copper catalyst and preparation method and application thereof Active CN114395769B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210111273.8A CN114395769B (en) 2022-01-29 2022-01-29 Supported copper catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210111273.8A CN114395769B (en) 2022-01-29 2022-01-29 Supported copper catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114395769A true CN114395769A (en) 2022-04-26
CN114395769B CN114395769B (en) 2023-07-11

Family

ID=81232438

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210111273.8A Active CN114395769B (en) 2022-01-29 2022-01-29 Supported copper catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114395769B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117821995A (en) * 2024-03-06 2024-04-05 内蒙古科技大学 Method for rapidly synthesizing heterostructure electrocatalyst by using Joule heat and application

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824165A (en) * 2017-04-17 2017-06-13 中国科学技术大学 The preparation method of CeO 2 supporting high-dispersion nano catalyst
CN106914237A (en) * 2017-02-28 2017-07-04 清华大学 A kind of monoatomic preparation method of metal
CN107774269A (en) * 2017-09-14 2018-03-09 天津大学 Co deposited synthesis copper ceria catalyst, preparation method and application
CN109954489A (en) * 2017-12-14 2019-07-02 中国科学院大连化学物理研究所 A kind of monatomic catalyst and its preparation and application
CN111530458A (en) * 2020-05-15 2020-08-14 江南大学 Monoatomic catalyst and application thereof in carbon dioxide hydrogenation reaction
CN112044434A (en) * 2020-10-20 2020-12-08 北京单原子催化科技有限公司 Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof
CN113332989A (en) * 2021-05-28 2021-09-03 浙江工业大学 Alumina supported copper-rare earth metal oxide catalyst and preparation method and application thereof
CN114293223A (en) * 2021-11-22 2022-04-08 江西师范大学 Method for preparing superfine cerium dioxide supported metal single-atom catalyst from cluster-based framework material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106914237A (en) * 2017-02-28 2017-07-04 清华大学 A kind of monoatomic preparation method of metal
CN106824165A (en) * 2017-04-17 2017-06-13 中国科学技术大学 The preparation method of CeO 2 supporting high-dispersion nano catalyst
CN107774269A (en) * 2017-09-14 2018-03-09 天津大学 Co deposited synthesis copper ceria catalyst, preparation method and application
CN109954489A (en) * 2017-12-14 2019-07-02 中国科学院大连化学物理研究所 A kind of monatomic catalyst and its preparation and application
CN111530458A (en) * 2020-05-15 2020-08-14 江南大学 Monoatomic catalyst and application thereof in carbon dioxide hydrogenation reaction
CN112044434A (en) * 2020-10-20 2020-12-08 北京单原子催化科技有限公司 Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof
CN113332989A (en) * 2021-05-28 2021-09-03 浙江工业大学 Alumina supported copper-rare earth metal oxide catalyst and preparation method and application thereof
CN114293223A (en) * 2021-11-22 2022-04-08 江西师范大学 Method for preparing superfine cerium dioxide supported metal single-atom catalyst from cluster-based framework material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHENXI ZHOU等: "Ultrasensitive lab-on-paper device via Cu/Co double-doped CeO2 nanospheres as signal amplifiers for electrochemical/visual sensing of miRNA-155", 《SENSORS AND ACTUATORS B: CHEMICAL》 *
GEORGIOS VARVOUTIS 等: "Remarkable efficiency of Ni supported on hydrothermally synthesized CeO2 nanorods for low-temperature CO2 hydrogenation to methane", 《CATALYSIS COMMUNICATIONS》 *
WEI LIU 等: "Transition metal-promoted oxidation catalysis by fluorite oxides: A study of CO oxidation over Cu-CeO2", 《THE CHEMICAL ENGINEERING JOURNAL》 *
WEILING YANG 等: "Effect of CeO2 preparation method and Cu loading on CuO/CeO2 catalysts for methane combustion", 《JOURNAL OF NATURAL GAS CHEMISTRY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117821995A (en) * 2024-03-06 2024-04-05 内蒙古科技大学 Method for rapidly synthesizing heterostructure electrocatalyst by using Joule heat and application

Also Published As

Publication number Publication date
CN114395769B (en) 2023-07-11

Similar Documents

Publication Publication Date Title
CN110227531B (en) Preparation method of molybdenum-doped cobalt-iron oxide nanosheet bifunctional electrocatalyst
CN109967099B (en) Co with hollow nano structure2P @ C composite material and preparation method and application thereof
CN111041517B (en) Preparation method and application of two-dimensional bismuth alkene nanosheet
CN112853379B (en) Preparation method and application of supported metal monatomic catalyst
CN111085195B (en) Metal alloy catalyst and preparation method thereof
CN106563450A (en) Preparation method of alpha phase cobaltous hydroxide nanosheet for oxygen evolution reaction
CN110538650B (en) Cerium oxide supported bismuth nano catalyst and preparation method and application thereof
CN110560075B (en) Nano Cu-Eu alloy catalyst with core-shell structure and preparation method and application thereof
CN111883785B (en) Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof
CN110302799B (en) Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method thereof
CN110152678A (en) A kind of electro-catalysis reduction CO2For the nanometer Cu-Yb alloy catalyst of the energy
CN114657592B (en) Nickel-based catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof
CN114293200A (en) Porous carbon loaded amorphous/crystalline ruthenium-based high-efficiency hydrogen evolution catalyst and preparation and application thereof
CN114395769A (en) Supported copper catalyst and preparation method and application thereof
CN116219480A (en) High-entropy alloy electrolyzed water catalyst and preparation method thereof
CN112921342B (en) CeO loaded2Hollow MnCo of nanoparticles2O4Preparation method of catalyst, obtained material and application
CN112281183B (en) Cluster-shaped bismuth selenide, preparation method thereof and application of cluster-shaped bismuth selenide in electrocatalytic reduction of carbon dioxide
CN113694928B (en) Metal catalyst and preparation method and application thereof
CN113846350A (en) Transition metal phosphide composite material for acidic electrolyzed water oxygen evolution and preparation method thereof
CN113774423A (en) Copper-based composite nano material and preparation method and application thereof
CN111063902A (en) Preparation method of nano metal intercalated hydrotalcite material electrode catalyst
CN112853378B (en) Preparation method of Bi-NC catalyst for carbon dioxide electroreduction
CN117512676B (en) Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof
CN114892203B (en) Method for synthesizing carbon monoxide by electrochemical catalytic conversion of carbon dioxide
CN115490258B (en) Copper oxide nano-sheet catalyst, preparation method and application thereof in electrocatalytic reduction of carbon dioxide and carbon monoxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant