CN109659571B - Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor - Google Patents

Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor Download PDF

Info

Publication number
CN109659571B
CN109659571B CN201910087391.8A CN201910087391A CN109659571B CN 109659571 B CN109659571 B CN 109659571B CN 201910087391 A CN201910087391 A CN 201910087391A CN 109659571 B CN109659571 B CN 109659571B
Authority
CN
China
Prior art keywords
reactor
carbon dioxide
electrode
catalyst
electrochemical reduction
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
CN201910087391.8A
Other languages
Chinese (zh)
Other versions
CN109659571A (en
Inventor
乔锦丽
刘俊宇
彭芦苇
吕丽
徐能能
王敏
郭晓晶
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.)
Institute Of Chemical Defense Chinese Academy Of Military Sciences
Donghua University
Original Assignee
Institute Of Chemical Defense Chinese Academy Of Military Sciences
Donghua 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 Institute Of Chemical Defense Chinese Academy Of Military Sciences, Donghua University filed Critical Institute Of Chemical Defense Chinese Academy Of Military Sciences
Priority to CN201910087391.8A priority Critical patent/CN109659571B/en
Publication of CN109659571A publication Critical patent/CN109659571A/en
Application granted granted Critical
Publication of CN109659571B publication Critical patent/CN109659571B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a carbon dioxide electrochemical reduction catalyst and application thereof in a zero-distance reactor. The zero-distance reactor has the advantages that the distances among the working electrodes, the membranes and the counter electrodes are close to zero, the reactor is similar to an MEA (membrane electrode assembly) type reactor, the structure is simple, the preparation materials are cheap, and the reactor can be used and operated very conveniently and quickly. The invention greatly shortens the distance between the electrodes, reduces ohmic polarization and electrochemical polarization, greatly improves the electrochemical performance, and improves the current efficiency and the energy efficiency in the reaction process.

Description

Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor
Technical Field
The invention belongs to the field of electrochemical reduction catalysts and preparation and application thereof, and particularly relates to a carbon dioxide electrochemical reduction catalyst and preparation and application thereof.
Background
With the burning of fossil fuels, the greenhouse effect and energy crisis are becoming more serious. In order to protect the earth, how to control the content of carbon dioxide in the atmosphere becomes a problem of great concern to human beings. Therefore, how to reduce and utilize carbon dioxide has become a focus of scientific research nowadays. Electrochemical reduction of carbon dioxide (ECR-CO)2) Has become a feasible method for controlling greenhouse effect and solving energy crisis. Generally, electrochemical reduction of carbon dioxide (ECR-CO)2) By a multiple electron reduction process in aqueous solution. The main products of electrochemical reduction of carbon dioxide are small organic compounds, such as formaldehyde (CH)2O), methane (CH)4) Formic acid (HCOOH), oxalic acid (H)2C2O4) Ethylene (C)2H4) Methanol (CH)3OH), ethanol (C)2H6O) and inorganic carbon monoxide (CO). However, since the electrochemical kinetics of carbon dioxide is slow, the carbon dioxide is often reduced by over-potential, which not only results in low energy utilization efficiency, but also produces hydrogen evolution effect to compete for reaction. Therefore, it is required to search for a catalyst having high activity or a more optimized reaction apparatus to solve this problem.
Metal organic framework of copper as a novel CO2Electrochemical reduction catalysts are reported. Compared with pure copper metal electrodes, the metal-organic framework of copper possesses a larger specific surface area and interconnected porous structure, has more stable electrochemical performance, and is non-toxic and environment-friendly [ Chemical Engineering Journal,313,1623(2017) ]]. However, the conventional electrochemical evaluation device is generally in an H-tank type electrolytic cell structure, and has great limitations, such as severe ohmic polarization and electrochemical polarization, and large energy loss generated in the reaction process [ chemistry electric, 1,6055(2016)]. Meanwhile, the traditional H-tank type electrolytic cell has single structure and air tightnessIn contrast, the connected portions of the reactor generate "dead zones", which seriously decrease the energy utilization efficiency of the reaction [ Electrochimica Acta,46,3015(2001)]。
Disclosure of Invention
The invention aims to solve the technical problem of providing a carbon dioxide electrochemical reduction catalyst, and preparation and application thereof, overcoming the defects of limitation and low energy utilization efficiency of an electrolytic cell structure in the prior art, and designing a novel fuel cell-like membrane electrode type zero-distance structure reactor. The reactor greatly shortens the distance between the working electrode and the counter electrode, thereby greatly improving the electrocatalysis of CO by the catalyst2The reduction performance, current efficiency and energy efficiency greatly reduce ohmic polarization and electrochemical polarization in the reaction process.
The invention relates to a carbon dioxide electrochemical reduction catalyst, which comprises a metal organic framework, wherein the metal organic framework is as follows: the copper-based catalyst is prepared by taking a copper source, benzenetricarboxylic acid and polyvinylpyrrolidone as raw materials through coprecipitation and calcination;
wherein the mass ratio of the copper source to the sum of the benzene tricarboxylic acid and the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1; the mass ratio of the benzenetricarboxylic acid to the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1.
The preparation method of the carbon dioxide electrochemical reduction catalyst comprises the following steps:
and mixing the copper source solution, the mixed solution of the benzene tricarboxylic acid and the polyvinylpyrrolidone, standing, centrifuging, cleaning, drying to obtain a catalyst precursor, and calcining to obtain the catalyst.
The preferred mode of the above preparation method is as follows:
the copper source is copper nitrate; the benzene tricarboxylic acid is trimesic acid, and the solvents of the copper source solution and the mixed solution are methanol.
The copper nitrate is copper nitrate trihydrate.
The mass ratio of the copper source to the sum of the benzene tricarboxylic acid and the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1; the mass ratio of the benzenetricarboxylic acid to the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1.
The calcination is specifically as follows: under the condition of protective gas, the heating rate is 1-20 ℃/min, the temperature is increased to 250-500 ℃, and the temperature is kept for 1-2 h.
A gas diffusion electrode of the present invention, wherein a surface of a substrate of the electrode supports the catalyst for electrochemical reduction of carbon dioxide according to claim 1.
The substrate is one of carbon paper, carbon felt, carbon cloth, a nano cellulose membrane, a nano biological membrane, a carbon nano tube and a graphene material.
The loading amount of the carbon dioxide electrochemical catalyst in the electrode is 1-15 mg/cm2。
The size of the gas diffusion electrode is 1.5cm multiplied by 2cm, and the mass of the carbon dioxide electrochemical reduction catalyst loaded on the gas diffusion electrode is 1.6-9.3mg/cm2。
The invention provides a preparation method of the gas diffusion electrode, which comprises the following steps: dispersing a carbon dioxide electrochemical reduction catalyst into an isopropanol solution, adding 1-8 wt% of a Nafion solution, carrying out ultrasonic treatment for 0.5-1h, coating the obtained mixed solution on a substrate, and drying to obtain the gas diffusion electrode loaded with the carbon dioxide electrochemical reduction catalyst.
The invention also provides a similar fuel cell membrane electrode MEA type zero-distance reactor, which comprises plates, electrodes and an ion exchange membrane, wherein a groove is arranged between the first plate and the second plate, a channel is arranged between the third plate, the ion exchange membrane is arranged in the channel, and a working electrode and a counter electrode are respectively arranged at the notch of the groove and are separated by the ion exchange membrane; wherein the working electrode is said gas diffusion electrode.
The board is ya keli plastic slab, connects with the silica gel gasket between three boards to prevent that electrolyte from leaking.
A small hole is formed above the first plate or the second plate and used for placing a reference electrode in the groove; the first plate and/or the second plate are/is provided with small holes for injecting electrolyte.
The working electrode and the counter electrode are connected to an electrochemical workstation through a metal platinum foil or a copper foil.
The ion exchange membrane is Nafion117 (DuPont, USA)
The method specifically comprises the following steps: a cathode groove and an anode groove of the reactor are respectively composed of three acrylic plates, wherein the first acrylic plate and the second acrylic plate have the same size, the length and the width are both 5cm, the height is 2cm, and a small groove with the length and the width of 2cm and the height of 1 cm is arranged between the two acrylic plates. The third acrylic plate has the same type, and is 5cm long and 5cm wide, and a square channel with 2cm long, 2cm wide and 1 cm high is arranged in the middle. The first and second acrylic plates have a hole at their edges for electrolyte injection and a hole above the first plate for placement of a reference electrode. A silica gel gasket is arranged in the middle of each piece of acrylic to prevent the electrolyte from leaking. The working electrode and the counter electrode are separated by an ion exchange membrane, and are connected to an electrochemical workstation through platinum foils or copper foils.
Advantageous effects
(1) The catalyst is a nano catalyst, and is synthesized by a coprecipitation method to form a copper metal organic framework structure with special appearance and multiple gaps. Compared with the existing reported metal organic framework structure, the catalyst has a spongy porous structure, so that the specific surface area of the catalyst is greatly improved, the electrochemical activity of the catalyst on carbon dioxide reduction is greatly improved, and the hydrogen evolution reaction is effectively inhibited;
(2) the catalyst disclosed by the invention is simple in preparation method, short in experimental period, low in price of required experimental materials and free of pollution, and has good application prospects in the fields of lithium ion batteries, carbon dioxide electrochemical reduction and the like;
(3) the reactor is a zero-distance reactor, when the carbon dioxide is electrochemically reduced, the distance between the working electrode, the membrane and the reference electrode is greatly shortened, the reaction efficiency can be obviously improved, the energy loss is reduced, and the promotion effect of the novel zero-distance reactor on the electrochemical reduction of the carbon dioxide is demonstrated in the figure 4 under the same catalyst conditionThe current density of the traditional H-type electrolytic cell is almost zero when the fixed electrolytic voltage is-0.8V, and the current density of the novel zero-distance reactor reaches 60mA/cm-2。
Drawings
FIG. 1 is a structural view of a conventional H-type electrolytic cell;
FIG. 2 is a structural diagram of a membrane electrode type zero-distance reactor of a fuel cell of this patent type;
FIG. 3 shows that the catalyst for electrochemical reduction of carbon dioxide of example 3 is applied to the reactor of example 5 in CO2Saturated 0.5MKHCO3And N2Saturated 0.5M KHCO3Cyclic voltammogram of (1);
FIG. 4 shows that the carbon dioxide electrochemical reduction catalyst of example 3 is applied to CO in examples 4 and 52Saturated 0.5MKHCO3Cyclic voltammogram of (1).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The preparation method of the copper metal organic framework catalyst precursor comprises the steps of dissolving 15.12g of copper nitrate trihydrate in 80mL of methanol solution to obtain solution A, dissolving 7.26g of trimesic acid and 1.7g of polyvinylpyrrolidone in 80mL of methanol solution to obtain solution B, using a disposable rubber head dropper to slowly drop the solution A into the solution B, placing the solution B into an ultrasonic machine to carry out ultrasonic treatment for 30min after dropping, taking out the solution and standing the solution for 5 hours, then using a centrifugal machine to centrifuge and wash the solution for 3 times with methanol, taking out the precipitate and placing the precipitate into a 60 ℃ oven to dry the precipitate for 12 hours. The obtained blue precipitate, which is the precursor of the copper metal organic framework catalyst, is called CuBTC catalyst.
Example 2
Will be described in example 1Grinding the prepared precursor into powder by using a mortar, placing the powder into a quartz boat, placing the quartz boat into a quartz tube of a tube furnace, introducing nitrogen for 1h, heating to 300 ℃ at the speed of 20 ℃/min, and maintaining for 2 h. And taking out after the temperature is reduced to room temperature to obtain black powder, namely the carbon dioxide electrochemical reduction catalyst which is called CuMOF-20-300 catalyst. Compared with the metal organic framework structure reported in the prior art, the catalyst has a porous sponge structure and more pores, so that the CO content can be improved2Adsorption and diffusion and mass transfer of electrolysis gas products.
Example 3
A gas diffusion electrode supporting a carbon dioxide electrochemical reduction catalyst, the gas diffusion electrode supporting the carbon dioxide electrochemical reduction catalyst described in example 2.
The gas diffusion electrode was a 1.5cm × 2cm H-090 type carbon paper electrode manufactured by Toray corporation of Japan. The preparation method of the gas diffusion electrode loaded with the carbon dioxide electrochemical reduction catalyst comprises the steps of dispersing 12mg of the copper metal organic framework synthesized in the example 2 into 800 mu L (mass fraction is 99.7%) of isopropanol solution, adding 80mg of Nafion solution with mass fraction of 5%, and obtaining a catalyst solution under the action of ultrasound. And (3) coating the catalyst solution on the gas diffusion electrode by using a trace liquid transfer gun, and drying the gas diffusion electrode in a drying oven at 60 ℃ for two hours to obtain the gas diffusion electrode loaded with the carbon dioxide electrochemical reduction catalyst. The loading capacity of the carbon dioxide electrochemical reduction catalyst is 3mg/cm2。
Example 4
An H-shaped electrolytic cell reactor with a metal organic framework of copper as the working electrode. The H-reactor was an electrolytic cell reactor for electrochemical performance testing using the gas diffusion electrode of example 3 as the working electrode. The reactor is a conventional H-type electrolytic cell, manufactured by Wuhan Gaoshi Rui-Co.
Example 5
A zero-distance reactor of the type of fuel cell Membrane Electrode (MEA) with a copper metal-organic framework as working electrode. The MEA reactor was a reactor in which electrochemical performance was tested using the gas diffusion electrode of example 3 as a working electrode. The reactor is a novel zero-distance reactor and is independently designed and manufactured by the applicant of the patent.
Conventional H-type reactors: the reactor consists of two electrolytic tanks, a gas diffusion electrode and an ion exchange membrane. The electrolytic cells are connected by a silica gel sheet and an ion exchange membrane. One of the gas diffusion electrodes serves as a working electrode and the other serves as a counter electrode, and the distance between the two electrodes is too large, so that a dead zone exists, as shown in FIG. 1.
And MEA-like zero-distance reactors: the reactor consisted of an acrylic plate, a sheet of silica gel, a gas diffusion electrode and an ion exchange membrane (Nafion117 (dupont, usa)). Each acrylic plate is separated by a silica gel sheet to prevent the acrylic plates from leaking in the reaction process. The CuMOF-loaded gas diffusion electrode is used as a working electrode and loaded with IrO2The gas diffusion electrode as a counter electrode is separated by an ion exchange membrane and sandwiched between silica gel plates to prevent leakage during the reaction process, as shown in FIG. 2.
The linear voltammogram of the invention is shown in FIGS. 3 and 4, and the apparatus used is a CHI760 electrochemical workstation manufactured by Chen Hua, Shanghai. FIG. 3 is a graph showing the linear voltammetry scans of the catalyst for electrochemical reduction of carbon dioxide in example 3 under carbon dioxide and nitrogen conditions in the reactor of example 5, and FIG. 3 illustrates that the reduction of carbon dioxide in the reactor of example 5 exhibits good activity, i.e., a current density of 50mA/cm under nitrogen-2The current density under the condition of carbon dioxide is 60mA/cm-2The novel zero-distance reactor can greatly improve the utilization rate of energy.
Fig. 4 shows the linear voltammetry scans of the carbon dioxide electrochemical reduction catalyst of example 3 applied to the reactors of examples 4 and 5, respectively, as shown in fig. 4: the new zero-distance reactor has the obvious promotion effect on the electrochemical reduction of the carbon dioxide under the same catalyst condition, namely, when the fixed electrolytic voltage is-0.8V, the current density of the traditional H-type electrolytic cell is only 20mA/cm-2And the current density of the novel zero-distance reactor reaches 60mA/cm-2. It is shown that the electrochemical characterization performance of the novel zero-distance reactor of example 5 is much higher than that of the conventional H-type electrolytic cell of example 4 under the same catalyst condition, i.e. the novel zero-distance reactor has a great promotion effect on carbon dioxide reduction.

Claims (4)

1. A kind of fuel cell membrane electrode MEA type zero distance reactor, the said reactor includes the board, electrode and ion exchange membrane, characterized by that, there are grooves in the middle of the first board and second board, there are channels in the middle of the third board, the ion exchange membrane is put into channel, working electrode and counter electrode locate the notch of groove separately, and separate with the ion exchange membrane; wherein the working electrode is a gas diffusion electrode; the plate is an acrylic plastic plate, and the three plates are connected by a silica gel gasket; the working electrode and the counter electrode are connected to an electrochemical workstation through a metal platinum foil or a copper foil; a small hole is formed above the first plate or the second plate and used for placing a reference electrode in the groove; the first plate and/or the second plate are/is provided with small holes for injecting electrolyte;
the gas diffusion electrode is a carbon dioxide electrochemical reduction catalyst loaded on the surface of a substrate, wherein the carbon dioxide electrochemical reduction catalyst is prepared by the following method: mixing a copper source solution, a mixed solution of benzene tricarboxylic acid and polyvinylpyrrolidone, standing, centrifuging, cleaning, drying to obtain a catalyst precursor, and calcining to obtain a catalyst; wherein the mass ratio of the copper source to the sum of the benzene tricarboxylic acid and the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1; the mass ratio of the benzenetricarboxylic acid to the polyvinylpyrrolidone is 0.1: 0.9-0.9: 0.1; the calcination is specifically as follows: under the condition of protective gas, the heating rate is 1-20 ℃/min, the temperature is increased to 250-300 ℃, and the temperature is kept for 1-2 h.
2. The reactor of claim 1, wherein the copper source is copper nitrate; the benzene tricarboxylic acid is trimesic acid, and the solvents of the copper source solution and the mixed solution are methanol.
3. The reactor of claim 1, wherein the substrate is one of carbon paper, carbon felt, carbon cloth, nano cellulose membrane, nano biological membrane, carbon nanotube, and graphene material; the loading capacity of the carbon dioxide electrochemical catalyst is 1-15 mg/cm2。
4. The reactor of claim 1, wherein the gas diffusion electrode is prepared by a method comprising: dispersing a carbon dioxide electrochemical reduction catalyst into an isopropanol solution, adding 1-8 wt% of a Nafion solution for ultrasonic treatment, coating the obtained mixed solution on a substrate, and drying to obtain the gas diffusion electrode loaded with the carbon dioxide electrochemical reduction catalyst.
CN201910087391.8A 2019-01-29 2019-01-29 Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor Active CN109659571B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910087391.8A CN109659571B (en) 2019-01-29 2019-01-29 Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910087391.8A CN109659571B (en) 2019-01-29 2019-01-29 Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor

Publications (2)

Publication Number Publication Date
CN109659571A CN109659571A (en) 2019-04-19
CN109659571B true CN109659571B (en) 2022-02-01

Family

ID=66122273

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910087391.8A Active CN109659571B (en) 2019-01-29 2019-01-29 Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor

Country Status (1)

Country Link
CN (1) CN109659571B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110756193B (en) * 2019-10-23 2021-09-07 东华大学 Carbon dioxide electrochemical reduction copper-indium bimetal co-doped organic framework catalyst and preparation method and application thereof
CN112305030B (en) * 2020-10-30 2021-06-15 东北石油大学 Electrochemical device for testing carbon dioxide reduction performance
CN113185399A (en) * 2021-04-30 2021-07-30 北京化工大学 Metal copper complex and application thereof in electrochemistry CO2Application in reduction

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966777A (en) * 2005-11-17 2007-05-23 上海空间电源研究所 Water electrolysis device with proton exchange membrane
CN103566934A (en) * 2013-10-30 2014-02-12 东华大学 Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof
WO2014056166A1 (en) * 2012-10-10 2014-04-17 南京工业大学 Method for preparing cu-btc and nano-cu-btc
CN204162485U (en) * 2014-09-11 2015-02-18 北京今大禹环保技术有限公司 A kind of organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption
CN106076260A (en) * 2016-06-15 2016-11-09 华南理工大学 A kind of room temperature fast preparation method of metallic organic framework oxidized graphite composite material
CN106423164A (en) * 2016-09-30 2017-02-22 上海理工大学 CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution
CN107774329A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of metal-organic framework materials and preparation method thereof
CN108588748A (en) * 2018-06-11 2018-09-28 浙江大学 A kind of method that Carbon dioxide electrochemical reduction prepares methane and ethylene
CN108770328A (en) * 2018-07-16 2018-11-06 安徽大学 Composite microwave absorbent and preparation method thereof derived from a kind of MOF
CN109174182A (en) * 2018-08-02 2019-01-11 南京工业大学 A kind of method and its application improving MOFs material catalytic oxidation activity

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103221126A (en) * 2011-03-31 2013-07-24 科学与工业研究委员会 Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966777A (en) * 2005-11-17 2007-05-23 上海空间电源研究所 Water electrolysis device with proton exchange membrane
WO2014056166A1 (en) * 2012-10-10 2014-04-17 南京工业大学 Method for preparing cu-btc and nano-cu-btc
CN103566934A (en) * 2013-10-30 2014-02-12 东华大学 Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof
CN204162485U (en) * 2014-09-11 2015-02-18 北京今大禹环保技术有限公司 A kind of organic wastewater with difficult degradation thereby apparatus for electrochemical treatment of less energy-consumption
CN106076260A (en) * 2016-06-15 2016-11-09 华南理工大学 A kind of room temperature fast preparation method of metallic organic framework oxidized graphite composite material
CN107774329A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of metal-organic framework materials and preparation method thereof
CN106423164A (en) * 2016-09-30 2017-02-22 上海理工大学 CuOx catalyst, preparation method of catalyst and application of catalyst in prevention and control of environmental pollution
CN108588748A (en) * 2018-06-11 2018-09-28 浙江大学 A kind of method that Carbon dioxide electrochemical reduction prepares methane and ethylene
CN108770328A (en) * 2018-07-16 2018-11-06 安徽大学 Composite microwave absorbent and preparation method thereof derived from a kind of MOF
CN109174182A (en) * 2018-08-02 2019-01-11 南京工业大学 A kind of method and its application improving MOFs material catalytic oxidation activity

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Surface polarization enhancement: high catalytic performance of Cu/CuOx/C nanocomposites derived from Cu-BTC for CO oxidation";Ruirui Zhang等;《J. Mater. Chem. A》;20160427(第4期);第8412–8420页 *
Ruirui Zhang等."Surface polarization enhancement: high catalytic performance of Cu/CuOx/C nanocomposites derived from Cu-BTC for CO oxidation".《J. Mater. Chem. A》.2016,(第4期),第8412–8420页. *

Also Published As

Publication number Publication date
CN109659571A (en) 2019-04-19

Similar Documents

Publication Publication Date Title
CN112062128B (en) Preparation method and application of nitrogen-doped porous carbon material based on crop straws
CN109659571B (en) Carbon dioxide electrochemical reduction catalyst and application thereof in zero-distance reactor
CN113737215B (en) Preparation method of nickel-iron-based nanosheet/foamed nickel oxygen evolution reaction electrode material
CN101814607A (en) Preparation method of platinum/graphen catalyst for proton exchange membrane fuel cell
CN103441287A (en) Preparation method of membrane electrode of direct methanol fuel cell
CN101667648B (en) Preparation method of water retention type proton exchange membrane for fuel cell
CN111584880B (en) Low-platinum proton exchange membrane fuel cell membrane electrode and preparation method thereof
CN105107539A (en) Graphene-iron-nitrogen codoped porous carbon composite catalyst for fuel cell and preparation method for graphene-iron-nitrogen codoped porous carbon composite catalyst
CN104716335B (en) A kind of flow battery electrode and preparation and application
CN108511777A (en) The construction method of proton exchange membrane with three-dimensional high-specific surface area surface and its high-performance membrane electrode based on this proton exchange membrane
CN114583191A (en) Method for preparing anode catalyst of direct methanol fuel cell by electrodeposition
Ünlü et al. Improved gas diffusion electrodes for hybrid polymer electrolyte fuel cells
CN103367768B (en) A kind of method preparing double-catalyst-layestructure structure of proton exchange membrane fuel cell
CN101162780A (en) Direct methanol fuel battery anode catalyst and method for producing the same
CN102916201A (en) Palladium-carbon nanocatalyst and preparation method thereof
CN102593475A (en) Modified Pt-based fuel-cell catalyst and preparation methods thereof
Li et al. Highly ordered 3D macroporous scaffold supported Pt/C oxygen electrodes with superior gas-proton transportation properties and activities for fuel cells
CN101176844B (en) Direct methanol fuel cell anode catalyzer as well as preparation method and application thereof
CN106299388B (en) A kind of biomass alkaline fuel cell air cathode and preparation method and application
CN101783409B (en) Preparation method of membrane electrode with negative pole being carbon-carried transition metal chelate catalytic agent
CN102357362A (en) Preparation method of anti-sulfide-poisoning fuel cell cathode catalyst
CN109888304A (en) A kind of preparation method of membrane electrode, preparation method and a kind of fuel cell and fuel cell
CN106328958A (en) Preparation method for membrane electrode of alkali anion exchange membrane fuel cell
CN113130913B (en) PtNPs/NiNPs/AgNWs/PET plastic electrode and application thereof in construction of fructose fuel cell
CN100486006C (en) Production method of membrane electrode of proton-exchange membrane fuel battery

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