CN113881955B - Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof - Google Patents

Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof Download PDF

Info

Publication number
CN113881955B
CN113881955B CN202111188530.XA CN202111188530A CN113881955B CN 113881955 B CN113881955 B CN 113881955B CN 202111188530 A CN202111188530 A CN 202111188530A CN 113881955 B CN113881955 B CN 113881955B
Authority
CN
China
Prior art keywords
carbon monoxide
copper
acetic acid
palladium
electrocatalyst
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.)
Active
Application number
CN202111188530.XA
Other languages
Chinese (zh)
Other versions
CN113881955A (en
Inventor
郑耿锋
纪亚丽
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.)
Fudan University
Original Assignee
Fudan University
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 Fudan University filed Critical Fudan University
Priority to CN202111188530.XA priority Critical patent/CN113881955B/en
Publication of CN113881955A publication Critical patent/CN113881955A/en
Application granted granted Critical
Publication of CN113881955B publication Critical patent/CN113881955B/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
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/089—Alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide

Abstract

The invention belongs to the technical field of electrocatalytic reduction of carbon monoxide, and particularly relates to an electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof. The invention firstly prepares an electrocatalyst-copper-palladium alloy nanoparticle electrocatalyst for electrocatalytically reducing carbon monoxide to generate acetic acid, then uses the electrocatalyst as a catalytic reaction cathode, adopts potassium hydroxide electrolyte to electrocatalytically reduce the carbon monoxide, and selectively generates acetic acid. The partial current density of acetic acid produced by electric reduction of carbon monoxide catalyzed by the catalyst can reach 425mA cm ‑2 The Faraday efficiency can reach 70%; the catalyst can continuously and stably run for 500 hours in a membrane electrode device with a total current of 2.5A, and meanwhile, the higher Faraday efficiency of acetic acid can be kept. The invention has the advantages of wide sources of raw materials, simple preparation method, environmental protection and low price, efficiently converts carbon monoxide into acetic acid, and has wide market application prospect.

Description

Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof
Technical Field
The invention belongs to the technical field of electrocatalytic reduction of carbon monoxide, and particularly relates to an electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof.
Background
Energy is one of the three major industries of the 21 st century, consuming a large amount of fossil fuel, and thus emitting a large amount of carbon dioxide (CO) 2 ) Greenhouse gases, which accelerate the global warming process very quickly. By utilizing an electrochemical technology, carbon dioxide greenhouse molecules can be efficiently converted into chemical energy to be stored in chemical fuel and products under the drive of clean, easily available and stable electric energy, and an important foundation is laid for reducing the utilization rate of fossil energy and realizing carbon peak and carbon neutralization. Carbon dioxide reduction in alkaline electrolytes can achieve higher conversion activity than in neutral or acidic electrolyte environments, however, CO 2 Is easy to react with alkaline electrolyte to cause a great deal of carbonic acidAccumulation of hydrogen salts affects the highly active conversion of carbon monoxide. Carbon monoxide is a key intermediate in the electrochemical reduction of CO2, and currently, commercial SOFC devices have been able to convert CO 2 High-efficient conversion to carbon monoxide in large scale. Therefore, the electrochemical catalytic reduction of carbon monoxide is directly carried out by a two-step method, so that the formation of byproduct bicarbonate can be avoided, the reaction is conveniently carried out by using an overbased electrolyte, and the larger current density is obtained.
Acetic acid is used as an important chemical, is widely applied to the important fields of polymer material manufacturing industry, food industry, medicine synthesis and the like, and has important significance in obtaining the acetic acid by electrochemical reduction of carbon monoxide. However, the Faraday efficiency of electrochemical reduction of carbon monoxide to acetic acid is still lower than 50%, and the partial current density is still lower than 200mA cm -2 Has a large gap from the level of industrial application. Ketene is reported to be an important intermediate for electrochemical reduction of carbon monoxide to acetic acid, while high carbon monoxide coverage favors electrochemical conversion of carbon monoxide to oxygenated products. Based on the above, the invention provides a new design idea of the catalyst. According to the invention, palladium is introduced into metallic copper, so that the coverage of carbon monoxide on a three-phase interface of catalytic reaction is improved, the stability of a ketene intermediate is enhanced, the selectivity and activity of catalyzing carbon monoxide to be reduced to acetic acid by a material are further enhanced, the current density of acetic acid component reaching the industrialization level is realized, and the catalyst designed by the invention has extremely high stability under the reaction condition, and can continuously and efficiently work for 500 hours. In addition, the catalyst designed by the invention has wide sources of raw materials, simple manufacturing process and convenient large-scale utilization.
Disclosure of Invention
The first object of the invention is to provide a catalyst for electrocatalytic reduction of carbon monoxide to acetic acid, which has high activity and high stability and is convenient for industrial use;
a second object of the present invention is to provide a novel and efficient catalyst preparation method for maximizing controllability of catalyst structure and active site density by forming intermetallic compounds.
A third object of the present invention is to provide a process for electrocatalytically reducing carbon monoxide to acetic acid using the catalyst.
The invention provides an electrocatalyst for electrocatalytically reducing carbon monoxide to generate acetic acid, which is copper-palladium alloy nano powder (particles) and is prepared by the following steps:
(1) Dissolving a copper salt precursor in ethylene glycol diethyl ether, and dissolving a palladium salt precursor in acetone;
(2) Stirring the above two solutions at room temperature for more than 5 min;
(3) After the two solutions are completely dissolved respectively, uniformly mixing the two solutions, and stirring for 1-180 minutes at room temperature;
(4) Preparing a sodium borohydride solution with the volume of about 5-1000 mL and the concentration of 0.1-10 mol/L, and dropwise adding the sodium borohydride solution into the mixed solution;
(4) After the sodium borohydride solution is added dropwise, stirring the solution at room temperature for 1-180 minutes to complete the reaction;
(5) After the reaction is finished, centrifuging the obtained solution to obtain black solid, washing the black solid with water and ethanol for a plurality of times, and then placing the black solid in a vacuum drying oven for drying to obtain disordered copper-palladium alloy nano powder;
(6) Placing the black copper-palladium alloy nano powder obtained by drying in a tube furnace, and using H 2 Calcining the Ar mixed atmosphere at 100-600 ℃ for 0.5-10 hours to obtain the copper-palladium intermetallic compound with orderly arranged atoms.
In the invention, the copper salt is one or more of copper chloride, copper acetate, copper sulfate and copper nitrate; the palladium salt is one or more of palladium chloride, palladium acetate, palladium sulfate and palladium nitrate.
The molar ratio of the copper salt to the palladium salt is 1 (0.1-10), preferably the molar ratio of the copper salt to the palladium salt is 1 (0.5-5), and more preferably the molar ratio of the copper salt to the palladium salt is 1 (0.8-2).
The copper-palladium alloy nanoparticle electrocatalyst is applied to electrocatalytic carbon monoxide reduction reaction to obtain two carbons and more than two carbons. Among them, the copper-palladium intermetallic compound has the highest reactive site density and the best electrocatalytic performance.
The method for generating acetic acid by electrocatalytic reduction of carbon monoxide by using the catalyst provided by the invention adopts potassium hydroxide electrolyte, and promotes electrocatalytic reduction of carbon monoxide to generate acetic acid by using stability of ketene intermediates and improvement of carbon monoxide coverage of a three-phase interface of catalytic reaction, and specifically comprises the following steps:
(1) Dispersing a copper-palladium alloy nanoparticle electrocatalyst in a solvent, adding a Nafion solution, and uniformly dispersing under ultrasonic conditions; spraying the catalyst layer by layer on the gas diffusion electrode by adopting a spraying mode, drying, and controlling the catalyst loading to be 0.1-1000 mg/cm 2 As an electrocatalytic reaction cathode;
(2) Introducing carbon monoxide gas to make carbon monoxide contact with one side of the electrode, which is not loaded with the electrocatalyst, and making potassium hydroxide electrolyte contact with one side of the electrode, which is loaded with the electrocatalyst; the electrode is subjected to hydrophobic treatment, carbon monoxide can penetrate through the electrode to be contacted with the catalyst, and electrolyte cannot diffuse to the other side;
(3) Applying negative voltage to the electrode, controlling the current to be 0.02-50A/cm 2 The carbon monoxide is selectively reduced to a main product acetic acid and other multi-carbon products (e.g., two and more carbon products), specifically one or more of ethylene, ethanol, ethylene, propanol; wherein the main product is acetic acid.
In the step (2), the carbon monoxide gas is introduced, and the flow rate is controlled to be 5mL/min to 1000 mL/min.
In the step (2), the electrolyte is a potassium hydroxide solution with the concentration of 1-10 mol/L.
The invention has the advantages that: the cathode catalyst can enhance the adsorption of carbon monoxide by materials, promote the coverage of carbon monoxide at a three-phase interface of catalytic reaction, stabilize ketene intermediates and promote the efficient reduction of carbon monoxide to acetic acid under mild conditions. Meanwhile, the combination of copper and palladium weakens the adsorption capacity of palladium to carbon monoxide, weakens the poisoning phenomenon of carbon monoxide, and enhances the stability of the catalyst under the reaction condition. The copper-palladium alloy nano electrocatalyst synthesized by the method has good chemical stability and electrocatalytic activity. The ratio of the copper-palladium two components, the applied potential, and the partial pressure of carbon monoxide in the reaction feed gas affect the product selectivity and partial current density of the carbon monoxide reduction. Therefore, the ratio of the copper-palladium two components is preferred in the present invention, preferably the applied potential and the partial pressure of carbon monoxide in the reaction feed gas.
The current density of the catalyst of the invention for catalyzing the electric reduction of carbon monoxide to generate acetic acid can reach 425mA cm -2 The Faraday efficiency can reach 70%, which is the highest value reported in the current literature; in addition, the catalyst can continuously and stably run for 500 hours in the membrane electrode device with the total current of 2.5A, and meanwhile, the higher Faraday efficiency of acetic acid can be kept. The invention has the advantages of wide sources of raw materials, simple preparation method, environmental protection and low price, and can lead the greenhouse gas carbon dioxide (CO) 2 ) The method can be used for efficiently converting carbon monoxide into acetic acid through a commercial Solid Oxide Electrolysis (SOEC) device, and has wide market application prospect.
Drawings
FIG. 1 is a schematic representation of the method of the present invention. The formation of copper palladium intermetallic compounds promotes improved coverage of carbon monoxide at the catalytic reaction interface and stabilizes ketene intermediates, thereby facilitating the catalytic reduction of carbon monoxide to acetic acid.
Fig. 2 shows the proportion of the invention as 1:1, and an X-ray diffraction image of a copper-palladium disordered alloy.
FIG. 3 is an X-ray diffraction image of the copper palladium intermetallic compound of the present invention.
FIG. 4 shows the morphology of the copper-palladium intermetallic compound nano electro-catalyst of the invention.
FIG. 5 is an elemental distribution image of a copper palladium intermetallic compound according to the present invention. Green is copper element and red is palladium element (scale 50 nm).
FIG. 6 is a line scan image of a transmission electron microscope element of the copper palladium intermetallic compound of the present invention.
In fig. 7, (a) is a high angle annular dark field scanning transmission electron microscope image of the copper palladium intermetallic compound of the invention, and (b) is an enlarged view of the image in the blue box in the drawing (a).
FIG. 8 is a graph showing the Faraday efficiency distribution and current density distribution of the product obtained by electrocatalytically reducing carbon monoxide with a copper-palladium intermetallic compound according to the invention.
FIG. 9 is a graph showing the stability of electrocatalytic reduction of carbon monoxide by copper palladium intermetallic compounds according to the present invention.
Detailed Description
The invention will be further illustrated by the following examples which will aid in the understanding of the invention but are not intended to limit the invention.
Example 1:
the ratio is 1:1, the preparation of the copper-palladium intermetallic compound electrocatalyst comprises the following specific steps:
(1) Disordered copper palladium alloy nano particles with the ratio of 1:1 are synthesized by a wet chemical method, and an X-ray diffraction image of the disordered copper palladium alloy nano particles is shown in figure 2. 1.5mmol of copper acetate was dissolved in 250mL of ethylene glycol diethyl ether, and 1.5mmol of palladium acetate was dissolved in 10mL of acetone. The solutions were stirred at room temperature for 30 minutes, respectively, and after complete dissolution, the solutions were mixed and stirred at room temperature for 30 minutes. 30mL of a sodium borohydride solution having a concentration of 1mol/L was added dropwise to the above mixed solution, and stirred while being added dropwise. After the completion of the dropwise addition, the above mixed solution was stirred at room temperature for another 10 minutes. The black precipitate was separated by centrifugation and washed several times with deionized water, ethanol, respectively. At 60 o And C, drying in a vacuum drying oven, and sealing and preserving the catalyst.
(2) The ratio of synthesis was 1:1 are arranged in a quartz tube of a tube furnace, and are arranged in H 2 Calcining at 300 deg.C for 3h in Ar atmosphere to obtain copper-palladium intermetallic compound with ordered atomic arrangement, and X-ray diffraction image is shown in figure 3.
Taking the copper-palladium intermetallic compound as an example, the morphology and element distribution of the copper-palladium intermetallic compound can be determined by a Transmission Electron Microscope (TEM) and a high-angle annular dark field scanning transmission electron microscope (HADDF-STEM). As can be seen from the TEM image of fig. 4, the material is a nanoparticle with a particle size of about several tens of nanometers; as can be seen from the element distribution image of fig. 5, copper elements and palladium elements in the material are uniformly distributed; as can be seen from the line scan of the transmission electron microscope element of fig. 6, the material is not subjected to element segregation; as can be seen from the HADDF-STEM element distribution picture of FIG. 7, copper atoms and palladium atoms are orderly arranged.
Secondly, in potassium hydroxide electrolyte, promoting electrocatalytic reduction of carbon monoxide to generate acetic acid, and specifically comprising the following steps:
the testing device adopts a flowing electrolytic cell of a three-electrode system. Preparation of a cathode: dispersing 20mg of the catalyst in 3ml of isopropanol solution by ultrasonic, adding 60 mu L of Nafion, and uniformly mixing by ultrasonic; uniformly spraying the solution on the surface of a gas diffusion electrode in a spraying mode, and controlling the loading of the catalyst to be 0.5mg/cm as a cathode of the reaction 2 . Preparation of anode: taking 20mg of commercial iridium trioxide powder, dispersing the commercial iridium trioxide powder in 3mL of isopropanol, adding 60 mu L of Nafion, and uniformly mixing by ultrasonic waves; uniformly spraying the solution on the surface of a gas diffusion electrode in a spraying mode, and controlling the loading amount of the iridium trioxide powder to be 0.5mg/cm as an anode for reaction 2 . A reference electrode: ag/AgCl electrode. Electrolyte solution: 1mol/L potassium hydroxide solution, and controlling the flow rate of the electrolyte to be 5mL/min. Reaction gas: high-purity CO gas, and controlling the flow rate of the gas at 40mL/min. In the reaction process, the electrochemical workstation is used for controlling the voltage applied to the cathode from minus 1.6 to minus 2.4V, and carbon monoxide is selectively reduced into a carbon two/carbon three product, wherein the main product is acetic acid. After the reaction was completed, 90% IR correction was performed according to a resistance of 1 ohm. After IR correction, the Faraday efficiency of acetic acid at a potential of-1.03V can reach 70%, and the current density of acetic acid can reach 425mA/cm -2 . The electrochemical properties are shown in FIG. 8.
Thirdly, the stability test of the catalyst under the reaction condition is carried out by utilizing a membrane electrode, and the specific steps are as follows:
a commercial membrane electrode system (two-electrode system) having an effective electrode area of 5cm was used 2 . Expanding a gas loaded with a copper-palladium intermetallic compoundThe bulk electrode was used as the cathode of the reaction, and the nickel mesh loaded with iridium trioxide was used as the anode of the reaction. The loading of the anode and cathode catalyst materials was controlled at 0.5mg/cm 2 Left and right. The current and potential of the reaction system are controlled by a direct current power supply, and the total current is 500mA/cm at 2.5 and 2.5A 2 The copper-palladium intermetallic compound synthesized by the invention realizes continuous and stable reaction for 500 hours at the current density, and the electrochemical stability curve is shown in figure 9. Meanwhile, the high acetic acid selectivity can be maintained, the electrochemical stability is excellent, and the application prospect is wide.
Example 2:
the ratio is 10:1, the preparation of the copper-palladium alloy electrocatalyst comprises the following specific steps:
synthesis 10 by wet chemistry: 1 proportion of copper palladium alloy nano particles. 1.5mmol of copper acetate was dissolved in 250mL of ethylene glycol diethyl ether, and 0.15 mmol of palladium acetate was dissolved in 1mL of acetone. The solutions were stirred at room temperature for 30 minutes, respectively, and after complete dissolution, the solutions were mixed and stirred at room temperature for 30 minutes. 15mL of 1mol/L sodium borohydride solution was added dropwise to the above mixed solution, with stirring. After the completion of the dropwise addition, the above mixed solution was stirred at room temperature for another 10 minutes. And (3) separating the black precipitate by centrifugation, and washing with deionized water and ethanol for 3-5 times respectively. At 60 o And C, drying in a vacuum drying oven, and sealing and preserving the catalyst.
And the ratio is 1:10, the preparation of the copper-palladium alloy electrocatalyst comprises the following specific steps:
synthesis 1 by wet chemistry: 10 proportion of copper palladium alloy nano particles. 0.15 mmol of copper acetate was dissolved in 25 mL ethylene glycol diethyl ether, and 1.5mmol of palladium acetate was dissolved in 10mL acetone. The solutions were stirred at room temperature for 30 minutes, respectively, and after complete dissolution, the solutions were mixed and stirred at room temperature for 30 minutes. A sodium borohydride solution of 15. 15mL concentration 1mol/L was added dropwise to the above mixed solution while stirring. After the completion of the dropwise addition, the above mixed solution was stirred at room temperature for another 10 minutes. And (3) separating the black precipitate by centrifugation, and washing with deionized water and ethanol for 3-5 times respectively.At 60 o And C, drying in a vacuum drying oven, and sealing and preserving the catalyst.
Third, the ratio of the catalyst to the electrocatalytic carbon monoxide reduction is 10:1 and 10:1, electrode preparation and electrochemical test of a copper-palladium alloy catalyst, which are specifically as follows:
the testing device adopts a flowing electrolytic cell of a three-electrode system. Preparation of a cathode: dispersing the catalyst 20mg in 3ml isopropanol solution by ultrasonic, adding 60 mu L Nafion, and uniformly mixing by ultrasonic; uniformly spraying the solution on the surface of a gas diffusion electrode in a spraying mode, and controlling the loading of the catalyst to be 0.5mg/cm as a cathode of the reaction 2 . Preparation of anode: dispersing 20mg commercial iridium trioxide powder in 3mL isopropanol, adding 60 mu L Nafion, and uniformly mixing by ultrasonic; uniformly spraying the solution on the surface of a gas diffusion electrode in a spraying mode, and controlling the loading amount of the iridium trioxide powder to be 0.5mg/cm as an anode for reaction 2 . A reference electrode: ag/AgCl electrode. Electrolyte solution: 1mol/L potassium hydroxide solution, and controlling the flow rate of the electrolyte to be 5mL/min. Reaction gas: the flow rate of the high-purity carbon monoxide gas is controlled at 40mL/min. In the reaction process, the electrochemical workstation is used for controlling the voltage applied to the cathode from minus 1.6 to minus 2.4V, and carbon monoxide is selectively reduced into a carbon two/carbon three product, wherein the main carbon monoxide reduction product is acetic acid.

Claims (5)

1. The method for generating acetic acid by electrocatalytic reduction of carbon monoxide is characterized in that copper-palladium alloy nano particles are used as a catalyst, and the catalyst is prepared by the following steps:
(1) Dissolving a copper salt precursor in ethylene glycol diethyl ether, and dissolving a palladium salt precursor in acetone;
(2) Stirring the above two solutions at room temperature for more than 5 min;
(3) After the two solutions are completely dissolved respectively, uniformly mixing the two solutions, and stirring for 1-180 minutes at room temperature;
(4) Preparing sodium borohydride solution with the volume of 5-1000 mL and the concentration of 0.1-10 mol/L, and dropwise adding the sodium borohydride solution into the mixed solution;
(4) After the sodium borohydride solution is added dropwise, stirring the solution at room temperature for 1-180 minutes to complete the reaction;
(5) After the reaction is finished, centrifuging the obtained solution to obtain black solid, washing the black solid with water and ethanol for a plurality of times, and then placing the black solid in a vacuum drying oven for drying to obtain disordered copper-palladium alloy nano powder;
(6) Placing the black copper-palladium alloy nano powder obtained by drying in a tube furnace, and using H 2 Calcining the Ar mixed atmosphere at 100-600 ℃ for 0.5-10 hours to obtain a copper-palladium intermetallic compound with orderly arranged atoms;
the method adopts potassium hydroxide electrolyte, utilizes the stabilization of ketene intermediate and the improvement of the coverage of carbon monoxide at a three-phase interface of catalytic reaction to promote electrocatalytic reduction of carbon monoxide to generate acetic acid, and comprises the following specific steps:
(1) Dispersing a copper-palladium alloy nanoparticle electrocatalyst in a solvent, adding a Nafion solution, and uniformly dispersing under ultrasonic conditions; spraying the catalyst layer by layer on the gas diffusion electrode by adopting a spraying mode, drying, and controlling the catalyst loading to be 0.1-1000 mg/cm 2 As an electrocatalytic reaction cathode;
(2) Contacting carbon monoxide with one side of the electrode without the electrocatalyst, and contacting potassium hydroxide electrolyte with one side of the electrode with the electrocatalyst; the electrode is subjected to hydrophobic treatment, carbon monoxide can penetrate through the electrode to be contacted with the catalyst, and potassium hydroxide electrolyte cannot diffuse to the other side;
(3) Applying negative voltage to the electrode, and controlling the current to be 0.02-5A/cm 2 Carbon monoxide is selectively reduced to acetic acid-based multi-carbon products;
the molar ratio of copper salt to palladium salt was 1:1.
2. The method according to claim 1, wherein the carbon monoxide gas is introduced in the step (2) at a flow rate of 5mL/min to 1000 mL/min.
3. The method of claim 1, wherein the concentration of the potassium hydroxide electrolyte in step (2) is 1-10 mol/L.
4. The process according to claim 1, wherein in step (3) the acetic acid-based multi-carbon product is in particular one or more of acetic acid, ethanol, ethylene, propanol; wherein the main product is acetic acid.
5. The method according to claim 1, wherein the copper salt is one or more of copper chloride, copper acetate, copper sulfate, copper nitrate; the palladium salt is one or more of palladium chloride, palladium acetate, palladium sulfate and palladium nitrate.
CN202111188530.XA 2021-10-12 2021-10-12 Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof Active CN113881955B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111188530.XA CN113881955B (en) 2021-10-12 2021-10-12 Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111188530.XA CN113881955B (en) 2021-10-12 2021-10-12 Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof

Publications (2)

Publication Number Publication Date
CN113881955A CN113881955A (en) 2022-01-04
CN113881955B true CN113881955B (en) 2023-06-27

Family

ID=79006379

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111188530.XA Active CN113881955B (en) 2021-10-12 2021-10-12 Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof

Country Status (1)

Country Link
CN (1) CN113881955B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115896838B (en) * 2022-12-06 2023-10-20 绍兴七轩新材料科技有限公司 Preparation and application of ionic liquid modified phthalocyanine metal electrode for preparing hydrogen peroxide by electrochemical oxygen reduction

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106180747A (en) * 2016-07-07 2016-12-07 王荔 A kind of palladium copper binary alloy nano material, its preparation method and reduce CO as catalyst electro-catalysis2application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106180747A (en) * 2016-07-07 2016-12-07 王荔 A kind of palladium copper binary alloy nano material, its preparation method and reduce CO as catalyst electro-catalysis2application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Electroreduction of carbon dioxide to hydrocarbons using bimetallic cu-pd catalysts with different mixing patterns;Sicao ma er. al.;《J. AM. CHEM. SOC.》;第139卷;47-50 *
Production of an ordered(B2) CuPd nanoalloy by low-temperature annealing under hydrogen atomsphere;Miho Yamauchi;《Dalton Trans.》;第40卷;4842-4845 *

Also Published As

Publication number Publication date
CN113881955A (en) 2022-01-04

Similar Documents

Publication Publication Date Title
Chen et al. Amination strategy to boost the CO 2 electroreduction current density of M–N/C single-atom catalysts to the industrial application level
Chen et al. Ir-based bifunctional electrocatalysts for overall water splitting
CN111001428B (en) Metal-free carbon-based electrocatalyst, preparation method and application
CN111921560B (en) Lattice-distorted ultrathin metal organic framework nanosheet catalyst, and preparation method and application thereof
CN111715245B (en) Based on high catalytic activity and crystalline RuTe 2 The electrolytic water catalyst and the preparation method thereof
CN113881955B (en) Electrocatalyst for electrocatalytic reduction of carbon monoxide to acetic acid and application thereof
CN111430737A (en) Copper-platinum alloy nanoparticle loaded nitrogen-doped three-dimensional porous carbon material and preparation method and application thereof
Zhu et al. Nanosized LaInO3 perovskite for efficient electrocatalytic reduction of CO2 to formate
CN113737218A (en) Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application
CN116145193B (en) Copper-based catalyst for electrocatalytic reduction of nitrate radical into ammonia and preparation method thereof
CN111589459A (en) Bifunctional catalyst for efficiently electrolyzing water, and preparation method and application thereof
CN114921796B (en) Dual-function self-supporting electrolyzed water catalytic material and preparation method and application thereof
Du et al. Catalysts and electrolyzers for the electrochemical CO 2 reduction reaction: from laboratory to industrial applications
CN114086202B (en) Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production
CN114808026A (en) Two-dimensional metal organic framework nanosheet supported noble metal monatomic catalyst and preparation method and application thereof
CN115404513A (en) Carbon-coated heterostructure electrocatalyst and preparation and application thereof
CN114774983A (en) Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof
CN115491699A (en) Nano copper-based catalyst, preparation method thereof and application of nano copper-based catalyst in electrocatalytic reduction of carbon dioxide and carbon monoxide
CN110721687A (en) Self-supporting porous Fe2O3Nanorod array electrocatalyst and preparation method thereof
CN115747874B (en) Preparation method and application of rare earth element doped 2D RE@Fe-MOF efficient integrated membrane electrode
Sun et al. Ultrafine iridium nanoparticles grown on sea urchin-like PdCu with boosted activity toward acidic oxygen evolution
CN114438538B (en) Electrocatalytic double-function material with few layers of tungsten disulfide anchored on surface of cobalt-nitrogen-doped carbon-based polyhedron and preparation method thereof
CN114214636B (en) Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode
CN115110113B (en) Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof
CN114291798B (en) Cobalt telluride nano rod electrocatalyst synthesized by microwave method and application thereof

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