CN109659571A - A kind of carbon dioxide electrochemical reduction catalyst and the application in zero distance reactor - Google Patents
A kind of carbon dioxide electrochemical reduction catalyst and the application in zero distance reactor Download PDFInfo
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- CN109659571A CN109659571A CN201910087391.8A CN201910087391A CN109659571A CN 109659571 A CN109659571 A CN 109659571A CN 201910087391 A CN201910087391 A CN 201910087391A CN 109659571 A CN109659571 A CN 109659571A
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- 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
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- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
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- H01M4/88—Processes of manufacture
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Abstract
The present invention relates to a kind of carbon dioxide electrochemical reduction catalyst and the application in zero distance reactor, it includes the metal organic frame of copper to carbon dioxide electrochemical reduction catalyst, calcines to obtain by tube furnace by Co deposited synthesis.Working electrode in zero distance reactor, film, and be a kind of reactor similar to MEA formula, and its structure is simple to the distance between electrode close to zero, it is cheap to prepare material, extremely can conveniently use and operation.The present invention greatly shortens the distance between electrode, reduces ohmic polarization and activation polarization, greatly improves chemical property, improves current efficiency and energy efficiency in reaction process.
Description
Technical field
The invention belongs to electrochemical reduction catalyst and its preparation and application field, in particular to a kind of carbon dioxide electrification
Learn reducing catalyst and its preparation and application.
Background technique
With the burning of fossil fuel, greenhouse effects and energy crisis are got worse.In order to preserve our planet, how to control big
The content of carbon dioxide becomes mankind's issues that need special attention in gas.Therefore, how to reduce and had become and work as using carbon dioxide
The focal issue of modern scientific research.Electrochemically reducing carbon dioxide (ECR-CO2) have become control greenhouse effects and solve the energy
The feasible method of crisis.In general, electrochemical reduction (the ECR-CO of carbon dioxide2) pass through polyelectron reduction side in aqueous solution
Method carries out.The primary product of Carbon dioxide electrochemical reduction is small molecular organic compounds, such as formaldehyde (CH2O), methane (CH4),
Formic acid (HCOOH), oxalic acid (H2C2O4), ethylene (C2H4), methanol (CH3OH), ethyl alcohol (C2H6) and inorganic matter carbon monoxide (CO) O.
However, usually needing high overpotential that could restore carbon dioxide since carbon dioxide electrochemical kinetics process is slow, not only causing
Efficiency of energy utilization is low, while generating liberation of hydrogen effect competitive reaction.Therefore, it is necessary to explore catalyst with high activity or more
The reaction unit of optimization is added to solve the problems, such as this.
The metal organic frame of copper is as a kind of novel CO2Electrochemical reduction catalyst is reported.With fine copper metal electricity
Pole is compared, and the metal organic frame of copper possesses bigger specific surface area and porous structure interconnected, and has more stable
Chemical property, and asepsis environment-protecting [Chemical Engineering Journal, 313,1623 (2017)].But mesh
Preceding Conventional electrochemical evaluating apparatus is usually H- groove profile electrolyser construction, and there are significant limitations, such as ohmic polarization and electrification
Serious polarization is learned, generates a large amount of energy loss [Chemistryselect, 1,6055 (2016)] during the reaction.Meanwhile
Its structure of traditional H- groove profile electrolytic cell is single, poor air-tightness, and the coupling part of reactor generates " dead zone ", serious to reduce instead
The energy utilization efficiency [Electrochimica Acta, 46,3015 (2001)] answered.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of carbon dioxide electrochemical reduction catalyst and its preparation and
Using the defect for overcoming limitation existing for electrolyser construction in the prior art, energy utilization efficiency low, the invention designs one
The novel types of fuel cells type membrane electrode formula zero distance structural response device of kind.The reactor highly shortened working electrode and right
The distance between electrode, to greatly improve catalyst electro-catalysis CO2The performance of reduction, current efficiency and energy efficiency,
Greatly reduce the ohmic polarization in reaction process and activation polarization.
A kind of carbon dioxide electrochemical reduction catalyst of the invention, the catalyst include metal organic frame, wherein
Metal organic frame are as follows: including copper source, benzenetricarboxylic acid, polyvinylpyrrolidone be raw material, be prepared by being co-precipitated, calcining
It arrives；
Wherein copper source and benzenetricarboxylic acid and polyvinylpyrrolidone quality and ratio be 0.1:0.9~0.9:0.1；Benzene three
The mass ratio of formic acid and polyvinylpyrrolidone is 0.1:0.9~0.9:0.1.
A kind of preparation method of carbon dioxide electrochemical reduction catalyst of the invention, comprising:
The mixed liquor of copper source solution, benzenetricarboxylic acid and polyvinylpyrrolidone is mixed, is stood, centrifugation, after cleaning
It is dry, catalyst precursor is obtained, calcines, obtains catalyst.
The preferred embodiment of above-mentioned preparation method is as follows:
Copper source is copper nitrate；Benzenetricarboxylic acid is trimesic acid, copper source solution, mixed liquor solvent be methanol.
The copper nitrate is Gerhardite.
Copper source and benzenetricarboxylic acid and polyvinylpyrrolidone quality and ratio be 0.1:0.9~0.9:0.1；Benzene three
The mass ratio of formic acid and polyvinylpyrrolidone is 0.1:0.9~0.9:0.1.
The calcining specifically: under the conditions of protective gas, heating rate is 1~20 DEG C/min, is warming up to 250~500 DEG C
And keep the temperature 1-2h.
The substrate surface of a kind of gas-diffusion electrode of the invention, the electrode loads carbon dioxide described in claim 1
Electrochemical reduction catalyst.
The substrate is carbon paper, carbon felt, carbon cloth, nano-cellulose film, nano biological film, carbon nanotube, grapheme material
One of.
The load capacity of carbon dioxide electrochemical catalyst is 1~15mg/cm in the electrode2。
The size of the gas-diffusion electrode is 1.5cm × 2cm, the carbon dioxide electrochemical reduction catalyst loaded thereon
Quality be 1.6-9.3mg/cm2。
The present invention provides a kind of preparation method of gas-diffusion electrode, comprising: urges Carbon dioxide electrochemical reduction
Agent is distributed in aqueous isopropanol, and the Nafion solution ultrasound 0.5-1h of 1wt%~8wt% is added, and resulting mixing is molten
Liquid is coated in substrate, drying, obtains the gas-diffusion electrode that load has carbon dioxide electrochemical reduction catalyst.
The present invention also provides a kind of types of fuel cells membrane electrode MEA formula zero distance reactors, and the reactor includes plate, electricity
Groove is equipped among pole and amberplex, first block of plate and second block of plate, third block plate centre is equipped with channel, ion exchange
Film is placed in channel, working electrode and is respectively arranged on groove notch to electrode, and is separated by with amberplex；Wherein working electrode
For the gas-diffusion electrode.
The plate is acrylic plastic plate, is connected between three blocks of plates with silica gel pad, to prevent electrolyte from leaking.
Aperture is equipped with for placing reference electrode in groove above described first piece or second block of plate；First block of plate and/
Or second block of plate is equipped with aperture, for injecting electrolyte.
The working electrode and electrochemical workstation is connected to by metal platinum foil or copper foil to electrode.
The amberplex is Nafion117 (DuPont Corporation)
Specifically: for types of fuel cells membrane electrode (MEA) formula zero distance reactor of Carbon dioxide electrochemical reduction, instead
The cathode can and anode slot for answering device are made of three pieces of acrylic boards respectively, wherein first piece and second piece of block acrylic board size phase
Together, length and width is 5 centimetres, is highly 2 centimetres, and having a length and width among two pieces of acrylic boards is 2 centimetres, high
Degree is 1 centimetre of little groove.Third block acrylic board model having the same, 5 centimetres long, 5 centimetres wide, centre has 2 lis one long
Rice, 2 centimetres wide, high 1 centimetre of square duct.Wherein there is aperture at the edge of first piece and second piece acrylic board, for injecting
Electrolyte has above first block of plate an aperture for being put into reference electrode.There is a silica gel pad in the centre of every piece of acrylic,
To prevent electrolyte from leaking.Working electrode and it is separated by between electrode with amberplex, working electrode and platinum is passed through to electrode
Foil or copper foil are connected to electrochemical workstation.
Beneficial effect
(1) catalyst of the invention is nanocatalyst, and by Co deposited synthesis, being formed has special appearance and mostly sky
The metal-organic framework of the copper of gap.Compared with the metal-organic framework of existing report, which has spongy
Multi-pore structure greatly improves the specific surface area of catalyst, greatly improves catalyst to the electricity of carbon dioxide reduction
Chemical activity effectively inhibits evolving hydrogen reaction；
(2) method for preparing catalyst of the invention is simple, and experimental period is short, and required experimental material is cheap, nothing
Pollution, catalyst of the invention have a good application prospect in fields such as lithium ion battery, Carbon dioxide electrochemical reductions；
(3) reactor of the invention is that zero distance formula reactor is greatly shortened in electrochemically reducing carbon dioxide
Working electrode, the distance between film and reference electrode can significantly improve reaction efficiency, reduce energy loss, as said in Fig. 4
It is bright under identical catalysts conditions, novel zero distance formula reactor promotes effect is aobvious to mention Carbon dioxide electrochemical reduction
It rises, i.e., when stationary electrolysis voltage is -0.8V, the current density of traditional H- type electrolytic cell is almost nil, and novel zero distance formula
The current density of reactor reaches 60mA/cm-2。
Detailed description of the invention
Fig. 1 is tradition H- type electrolyser construction figure；
Fig. 2 is this patent types of fuel cells membrane electrode formula zero distance structure of reactor figure；
Fig. 3 is that the carbon dioxide electrochemical reduction catalyst of embodiment 3 applies to 5 reactor of embodiment in CO2Saturation
0.5MKHCO3And N2The 0.5M KHCO of saturation3In cyclic voltammetry curve comparison diagram；
Fig. 4 is that the carbon dioxide electrochemical reduction catalyst of embodiment 3 applies to embodiment 4 and embodiment 5 in CO2Saturation
0.5MKHCO3In cyclic voltammetry curve figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The preparation of the metal organic frame catalyst precursor of copper: 15.12g Gerhardite is taken to be dissolved in 80mL methanol molten
It is referred to as solution A in liquid, then 7.26g trimesic acid and 1.7g polyethylene pyrrole network alkanone is taken to be dissolved in 80mL methanol solution together
Solution A is slowly dropped in B solution by referred to as B solution then with disposable rubber head dropper, is put into after being added dropwise super
Ultrasound 30min in sound machine stands 5 hours after taking-up, and then with centrifuge centrifugation, simultaneously methanol is washed 3 times, and precipitating is taken to be put into 60
DEG C baking oven in dry 12 hours.Obtained blue precipitate, the as presoma of the metal organic frame catalyst of copper, referred to as
CuBTC catalyst.
Embodiment 2
The presoma mortar grinder prepared in embodiment 1 is put into quartz boat at powder, and quartz boat is put into
In the quartz ampoule of tube furnace, then first lead to nitrogen 1h, then be warming up to 300 DEG C with the rate of 20 DEG C/min and maintain 2h.Wait temperature
Degree takes out after being reduced to room temperature, obtains black powder, as carbon dioxide electrochemical reduction catalyst, referred to as CuMOF-20-300
Catalyst.Compared with the metal-organic framework of existing report, which is presented cellular cavernous structure, has more
Hole, so as to improve to CO2Absorption and water electrolytic gas product diffusion and mass transfer.
Embodiment 3
A kind of to load the gas-diffusion electrode for having carbon dioxide electrochemical reduction catalyst, loading in gas-diffusion electrode has
Carbon dioxide electrochemical reduction catalyst as described in example 2.
The H-090 type carbon paper electrode that the Japanese Toray company that gas-diffusion electrode is 1.5cm × 2cm produces.Described is negative
Be loaded with the gas-diffusion electrode of carbon dioxide electrochemical reduction catalyst in 12mg embodiment 2 the preparation method comprises the following steps: will synthesize
The metal organic frame of copper is distributed in (mass fraction 99.7%) aqueous isopropanol of 800 μ L, and 80mg mass fraction is added
For 5% Nafion solution, catalyst solution is obtained under ultrasonication.Above-mentioned catalyst solution is taken to smear with micropipette rifle
To gas-diffusion electrode, after being put into baking oven 60 DEG C of drying two hours, obtaining load has Carbon dioxide electrochemical reduction catalysis
The gas-diffusion electrode of agent.Carbon dioxide electrochemical reduction catalyst carrying capacity is 3mg/cm2。
Embodiment 4
A kind of working electrode is the H- type electrolytic cell reactor of the metal organic frame of copper.The H-type reactor is will
Gas-diffusion electrode in embodiment 3 carries out the electrolytic cell reactor of electrochemical property test as working electrode.Described is anti-
Answering device is traditional H- type electrolytic cell, is manufactured by Wuhan Grolsch Rui Lian Science and Technology Ltd..
Embodiment 5
A kind of working electrode is types of fuel cells membrane electrode (MEA) formula zero distance reactor of the metal organic frame of copper.
The MEA formula reactor is to carry out electrochemical property test for the gas-diffusion electrode in embodiment 3 as working electrode
Reactor.The reactor is novel zero distance formula reactor, is made by applicant autonomous Design.
Traditional H- type reactor: reactor is made of two electrolytic cells, gas-diffusion electrode and amberplex.Electrolysis
It is connected by silica gel piece with amberplex between slot.Gas-diffusion electrode one is used as working electrode, another is used as to electrode,
Distance is excessive between two electrodes, exists simultaneously " dead zone ", as shown in Figure 1.
And class MEA formula zero distance reactor: reactor is handed over by acrylic board, silica gel piece, gas-diffusion electrode and ion
Change film (Nafion117 (DuPont Corporation)) composition.It is separated between each piece of acrylic board by silica gel piece, prevents it from reacting
Leakage in the process.The gas-diffusion electrode of loaded Cu MOF loads IrO as working electrode2Gas-diffusion electrode be used as to electricity
Pole, centre is separated by amberplex, and is clipped among silica gel plate and is prevented its leakage during the reaction, as shown in Figure 2.
The linear voltammetric scan figure of the present invention is as shown in Figure 3 and Figure 4, and instrument is the model of Shanghai Chen Hua company production
CHI760 electrochemical workstation.Shown in Fig. 3 be respectively embodiment 3 in carbon dioxide electrochemical reduction catalyst apply to reality
The linear voltammetric scan curve in 5 reactor of example under carbon dioxide conditions and under condition of nitrogen gas is applied, attached drawing 3 illustrates in embodiment
Carbon dioxide reduction shows good activity in 5 reactors, i.e., current density is 50mA/cm under condition of nitrogen gas-2, in titanium dioxide
Current density is 60mA/cm under the conditions of carbon-2, illustrate that novel zero distance formula reactor can greatly improve the utilization rate of energy.
Shown in Fig. 4 be respectively embodiment 3 in carbon dioxide electrochemical reduction catalyst apply to embodiment 4 and implement
The linear voltammetric scan curve of reactor in example 5, as shown in Figure 4: illustrating under identical catalysts conditions, novel zero distance formula
Reactor promotes effect is aobvious to be promoted Carbon dioxide electrochemical reduction, i.e., when stationary electrolysis voltage is -0.8V, traditional H- type
The current density of electrolytic cell is only 20mA/cm-2, and the current density of novel zero distance formula reactor reaches 60mA/cm-2.Explanation
In the identical situation of catalyst, the electrochemical Characterization performance of the novel zero distance formula reactor of embodiment 5 is significantly larger than implemented
The electrochemical Characterization performance of traditional H- type electrolytic cell in example 4, i.e., novel zero distance formula reactor have carbon dioxide reduction
Greatly facilitate effect.
Claims (10)
1. a kind of carbon dioxide electrochemical reduction catalyst, which is characterized in that the catalyst includes metal organic frame, metal
Organic frame are as follows: including copper source, benzenetricarboxylic acid, polyvinylpyrrolidone be raw material, be prepared by being co-precipitated, calcining；Its
Middle copper source and benzenetricarboxylic acid and polyvinylpyrrolidone quality and ratio be 0.1:0.9~0.9:0.1；Benzenetricarboxylic acid and poly- second
The mass ratio of alkene pyrrolidone is 0.1:0.9~0.9:0.1.
2. a kind of preparation method of carbon dioxide electrochemical reduction catalyst described in claim 1, comprising:
The mixed liquor of copper source solution, benzenetricarboxylic acid and polyvinylpyrrolidone is mixed, is stood, centrifugation is dry after cleaning,
Catalyst precursor is obtained, calcines, obtains catalyst.
3. preparation method according to claim 2, which is characterized in that copper source is copper nitrate；Benzenetricarboxylic acid is equal benzene three
Formic acid, copper source solution, mixed liquor solvent be methanol.
4. preparation method according to claim 2, which is characterized in that the calcining specifically: under the conditions of protective gas, heating
Rate is 1~20 DEG C/min, is warming up to 250~500 DEG C and keeps the temperature 1-2h.
5. a kind of gas-diffusion electrode, which is characterized in that carbon dioxide described in the substrate surface load claim 1 of the electrode
Electrochemical reduction catalyst.
6. gas-diffusion electrode according to claim 5, which is characterized in that the substrate is carbon paper, carbon felt, carbon cloth, nanometer
One of cellulose membrane, nano biological film, carbon nanotube, grapheme material；The load capacity of carbon dioxide electrochemical catalyst
For 1~15mg/cm2。
7. a kind of preparation method of gas-diffusion electrode described in claim 5, comprising: by carbon dioxide electrochemical reduction catalyst
It is distributed in aqueous isopropanol, the Nafion solution ultrasound of 1wt%~8wt% is added, resulting mixed solution is coated to base
On bottom, drying obtains the gas-diffusion electrode that load has carbon dioxide electrochemical reduction catalyst.
8. a kind of types of fuel cells membrane electrode MEA formula zero distance reactor, the reactor includes plate, electrode and ion exchange
Film, which is characterized in that groove is equipped among first block of plate and second block of plate, third block plate centre is equipped with channel, amberplex
It is placed in channel, working electrode and groove notch is respectively arranged on to electrode, and be separated by with amberplex；Wherein working electrode is
Gas-diffusion electrode described in claim 5.
9. reactor according to claim 8, which is characterized in that the plate is acrylic plastic plate, with silicon between three blocks of plates
Glue gasket connection；Working electrode and electrochemical workstation is connected to by metal platinum foil or copper foil to electrode.
10. reactor according to claim 8, which is characterized in that be equipped with aperture above described first piece or second block of plate and use
In placement reference electrode in groove；First block of plate and/or second block of plate are equipped with aperture, for injecting electrolyte.
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Cited By (3)
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| CN110756193A (en) * | 2019-10-23 | 2020-02-07 | 东华大学 | Carbon dioxide electrochemical reduction copper-indium bimetal co-doped organic framework catalyst and preparation method and application thereof |
| CN112305030A (en) * | 2020-10-30 | 2021-02-02 | 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 |
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| CN110756193A (en) * | 2019-10-23 | 2020-02-07 | 东华大学 | Carbon dioxide electrochemical reduction copper-indium bimetal co-doped organic framework catalyst and preparation method and application thereof |
| CN112305030A (en) * | 2020-10-30 | 2021-02-02 | 东北石油大学 | Electrochemical device for testing carbon dioxide reduction performance |
| 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 |
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