CN108441878A - A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst and the preparation method and application thereof - Google Patents
A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst and the preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The invention discloses a kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalysts and its preparation method and application, the nanometer tin-based catalyst is the one-dimentional structure being made of tin dioxide nanometer tube and stannic oxide nano wire, and the tin dioxide nanometer tube is set in outside the stannic oxide nano wire.The nanometer tin-based catalyst is prepared through a step electrostatic spinning process combination calcination processing.The nanometer tin-based catalyst of the special appearance can be used for catalytic electrochemical reduction carbon dioxide reaction, significantly improve the faradic efficiency and current density of the reaction.
Description
Technical field
The present invention relates to electro-catalysis reduction carbon dioxide fields, and in particular to a kind of electrochemically reducing carbon dioxide reaction use
Nanometer tin-based catalyst and the preparation method and application thereof.
Background technology
Continuous rising in view of carbon dioxide content in air leads to climate change, using advanced technology by carbon dioxide
It is desirable to carry out conversion.One ideal solution is the carbon by the carbon dioxide conversion in air at higher energy density
One product, such as：Regenerative resource workable for carbon monoxide, formic acid, methanol, methane etc..This strategy can not only be reduced
Carbon dioxide accumulates in an atmosphere, and can produce fuel and useful industrial chemistry substance, to alleviate us to traditional
The dependence of fossil resource.For this purpose, the restoring method of various carbon dioxide, including electrochemistry, photochemistry, biochemistry and heat chemistry
Method has been suggested and has been had made intensive studies to it.In these methods, electrochemically reducing carbon dioxide is especially attractive,
Because it has higher efficiency, controllable selectivity, simple reaction member, and with the huge of actual industrialization application
Potentiality.Moreover, carbon dioxide electroreduction can also be considered as a short-cut method for storing renewable resource with chemical species.
In addition to this, Carbon dioxide electrochemical reduction can also be directly with other new energy, such as solar power generation, and wind-power electricity generation mutually ties
It closes.
But there is also several main key scientific challenges for electrochemically reducing carbon dioxide：1) because forming key intermediate species
Energy barrier it is high, reduction process needs higher overpotential, and the energy efficiency of this meaning reduction process is relatively low；2) due to carbon dioxide
Electrochemical reduction dynamics carries out slow obstacle and carbon dioxide is transmitted to the limitation of electrochemical catalyst surface energy, electrification
It is at a fairly low to learn reaction rate；3) a variety of gaseous states and liquefied mixture be can get from carbon dioxide reduction product, in such case
Under, the separation costs of product are higher；4) during the reaction, the catalytic activity position of electrochemical catalyst can be produced by centre
Object, by-product and the impurity in electrolyte are poisoned or are blocked, and cause catalyst life shorter；5) carbon dioxide reduction
It carries out in aqueous solution, it is contemplated that the competition of evolving hydrogen reaction.The side reaction important as one, it is usually lower
Occur under potential, it has a significant impact to the selectivity of faradaic efficiency and electrochemical catalyst.
By the modification to catalyst, it can effectively increase the activity of electrochemically reducing carbon dioxide.Au catalyst, silver
Catalyst, palladium catalyst etc. are used to electrochemically reducing carbon dioxide, but these catalyst are expensive, it is difficult to by industrializing
Using.Tin-based catalyst is a kind of selection well, and tin rich reserves are cheap, and can restore carbon dioxide simultaneously
To formic acid and carbon monoxide.Many tinbase electrochemically reducing carbon dioxide catalyst are devised, including tin oxide restores
The tin arrived, tinfoil paper etc..
As Publication No. CN 103715436A Chinese patent literature in disclose a kind of Carbon dioxide electrochemical reduction and urge
Agent, the stannic oxide nanometer to be synthesized by hydro-thermal reaction are spent.The for another example Chinese patent of Publication No. CN 105680061A
A kind of carbon dioxide electrochemical reduction catalyst is disclosed in document, includes that the coralloid nano oxidation with multilevel hierarchy is sub-
Tin, the catalyst are also prepared by hydro-thermal reaction.
But the selectivity of tin-based catalyst prepared by the above method is all not good enough, and the faradic efficiency of product is usually less than
90%；Current density also very little, usually less than 10mA cm-2。
Invention content
The present invention in view of the above technical problems, discloses a kind of nanometer of tin-based catalyst, can be used for catalytic electrochemical reduction
Carbon dioxide reaction significantly improves the faradic efficiency and current density of the reaction.
Specific technical solution is as follows：
A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst, for by tin dioxide nanometer tube and titanium dioxide
The one-dimentional structure of stannum nanowire composition, the tin dioxide nanometer tube are set in outside the stannic oxide nano wire.
Preferably, the length of the tin dioxide nanometer tube is 1~10 micron, draw ratio is 2~20；
The length of the stannic oxide nano wire is 1~10 micron, draw ratio is 5~50.
The nanometer tin-based catalyst of the special appearance increases the specific surface area of catalyst, increases catalytic reaction activity position
Point, catalyst surface have abundant grain boundary structure, can effectively increase the activity of electro-catalysis reduction carbon dioxide.
The invention also discloses the preparation methods of the nanometer tin-based catalyst, and steps are as follows：
(1) pink salt, high polymer are mixed with mixed solvent and obtains spinning solution, it is thin to obtain composite fibre through electrostatic spinning process
Film；
The mixed solvent is made of solvent A and solvent B, and the difference of the boiling point of solvent A and the boiling point of solvent B is 10~80
℃；
(2) composite fiber thin film prepared by step (1) is subjected to high-temperature calcination in air atmosphere, obtains the nanometer
Tin-based catalyst.
The nanometer tin-based catalyst with special appearance, the preparation process is prepared using electrostatic spinning process in the present invention
Key be the selection of mixed solvent, select the solvent with boiling point difference, can make in nanofiber in calcination process
Portion's unbalance stress one promotes the generation of pipe-linear structure.
In step (1)：
Presoma of the pink salt as tin in the present invention, it is desirable that in the mixed solvent different solubility.It is selected from but not limited to
Stannous chloride, stannous acetate, stannous sulfate；
High polymer in the present invention is selected from but not limited to selected from polyvinylpyrrolidone, gathers for disperseing tinbase presoma
Acrylonitrile, polystyrene, polyvinyl alcohol, polypropylene.
Preferably, in the spinning solution, the mass fraction of pink salt is 5~20%, the mass fraction of high polymer is 5~
20%.Further preferably, in the spinning solution, the mass ratio of pink salt and high polymer is 0.25~4：1；Further preferably, pink salt and height
The mass ratio of polymers is 1：1.
In the present invention, the composition of mixed solvent is most important for the pattern of final products, preferably, the mixing is molten
Agent is selected from ethyl alcohol/N,N-dimethylformamide, ethanol/water, water/N,N-dimethylformamide, ethyl alcohol/dimethyl sulfoxide (DMSO), N, N-
Dimethylformamide/dimethyl sulfoxide (DMSO)；Water/dimethyl sulfoxide (DMSO)；
The volume ratio of the in the mixed solvent, solvent A and solvent B are 0.1~10：1.
Further preferably, the mixed solvent is selected from ethyl alcohol/n,N-Dimethylformamide.
Preferably, the technique of the electrostatic spinning is：
Voltage is 15kV, and distance is 15cm.
In step (2)：
The use of the high-temperature calcination technique and mixed solvent, jointly promotes the generation of pipe-linear structure, high-temperature calcination
By controlling the evaporation rate of mixed solvent, the time of unbalance stress one inside nanofiber can be controlled, and then control catalysis
The pattern of agent.Preferably, the temperature of the high-temperature calcination is 350~650 DEG C, the time is 1~5h.
The invention also discloses a kind of electrochemically reducing carbon dioxide reaction electrodes, including electrode holder, will be described
Nanometer tin-based catalyst is carried on the electrode holder, and load capacity is 0.1~10mg cm2。
Compared with prior art, the present invention has the following advantages：
1, electrochemically reducing carbon dioxide disclosed by the invention reaction nanometer tin-based catalyst, have by nanotube with receive
The one-dimentional structure of rice noodles composition, and nanotube is set in outside nano wire.The structure can increase the specific surface area of catalyst, increase
Add catalytic reaction activity site；Catalyst surface has abundant grain boundary structure, can effectively increase catalyst electro-catalysis also
The activity of former carbon dioxide.
2, the present invention is obtained by the mixed solvent of the special composition of screening through a step electrostatic spinning process, then through calcination processing
To the nanometer tin-based catalyst of above-mentioned special appearance, the preparation process is simply, controllably.
3, the nanometer tin-based catalyst with special appearance for preparing the present invention is anti-for electrochemically reducing carbon dioxide
It answers, can be efficiently by carbon dioxide reduction to carbon one product, including formic acid, carbon monoxide etc., faradic efficiency is up to 93%,
Current density is up to 13mAcm-2。
Description of the drawings
Fig. 1 is stereoscan photograph of the nanometer tin-based catalyst of the preparation of embodiment 1 under different amplification；
Fig. 2 is transmission electron microscope photo of the nanometer tin-based catalyst of the preparation of embodiment 1 under different amplification；
Fig. 3 is nanometer tin-based catalyst (curve 1) and common tin oxide nano particles catalyst prepared by embodiment 1
Catalytic performance comparison diagram；
Fig. 4 is nanometer tin-based catalyst (curve 1) and common tin oxide nano particles catalyst prepared by embodiment 1
Current density comparison diagram.
Specific implementation mode
For a further understanding of the present invention, a kind of nanometer of tin-based catalyst provided by the invention is carried out with reference to example
It specifically describes, but the present invention is not limited to these Examples, what the skilled artisan made under core guiding theory of the present invention
Non-intrinsically safe is modified and adjusts, and still falls within protection scope of the present invention.
Embodiment 1
(1) 1.0g polyvinylpyrrolidones (PVP, Mw=1,300,000) are dissolved in 1.0g stannous chloride dihydrates
5ml dimethylformamides (DMF) stir obtain spinning solution afterwards for 24 hours at room temperature, be transferred into 5ml alcohol mixed solvents
It in syringe, is placed on syringe pump, one block of conductive charcoal is placed at 18cm over there, as electrostatic spinning reception device.By high pressure
Power supply is connected on syringe needle, and ground wire is connected on conductive charcoal.Apply 15kV high pressures, injection flow rate pump is 0.3ml h-1, receive
Stannous chloride/polyvinylpyrrolidone/dimethylformamide/ethyl alcohol composite fiber thin film is obtained after collection 4h.
(2) composite fiber thin film obtained by step (1) is placed in tube furnace and calcines 2h in air atmosphere, calcination temperature
It it is 500 DEG C, heating rate is 5 DEG C of min-1.Polyvinylpyrrolidone/dimethylformamide/ethyl alcohol will decompose, stannous chloride two
Hydrate is oxidized to stannic oxide, and a nanometer tin-based catalyst, stereoscan photograph such as Fig. 1 institutes of the catalyst is prepared
Show, transmission electron microscope photo is as shown in Figure 2.It has been observed that nanotube length is~10 microns, draw ratio 20；Nanowire length
It is 10 microns, draw ratio 50；With abundant grain boundary structure.
(3) catalyst and 100 μ L 5%Nafion solution, 1ml ethyl alcohol 10mg steps (2) being prepared mix and surpass
Sound disperses, and 100 μ L dispersant liquid drops are then added in 1cm2Carbon paper on, at 60 DEG C dry.It is prepared and is used for electrochemical reduction
The load capacity of the electrode of carbon dioxide, catalyst is 1mg cm-2。
(4) electrode for preparing step (3) is as working electrode, and platinum electrode is used as to electrode, and Ag/AgCl electrodes are as ginseng
Than electrode, electrochemically reducing carbon dioxide is carried out in H bottles, electrolyte is 0.1M KHCO3, H bottles it is intermediate using Nafion membrane every
It opens.Gaseous product is quantified using gas-chromatography, nuclear magnetic resonance spectroscopy is quantitative for liquid product.
Through step (4), can calculate nanometer tin-based catalyst electro-catalysis restore carbon dioxide to one product of carbon (formic acid with
Carbon monoxide) faradic efficiency, up to 93% (curve 1), as shown in figure 3, (bent far above common tin oxide nano particles
Line 2).
The current density of nanometer tin-based catalyst electro-catalysis reduction carbon dioxide is 12mA cm-2(curve 1), such as Fig. 4 institutes
Show, is far above common tin oxide nano particles (curve 2).
Common tin oxide nano particles are commercially available, prepare electrode with common tin oxide nano particles and are with the electrode
The process of working electrode progress electrochemically reducing carbon dioxide reaction is with embodiment 1 in the identical of record.
Embodiment 2
(1) by 2.0g polyacrylonitrile (PAN, Mw=1,500,00) and 2.0g stannous acetate 3ml n,N-Dimethylformamide
With 7ml dimethyl sulfoxide (DMSO) in the mixed solvents, stirs obtain spinning solution afterwards for 24 hours at room temperature, be transferred into syringe, be placed in
On syringe pump, one block of conductive charcoal is placed at 18cm over there, as electrostatic spinning reception device.High voltage power supply is connected on syringe
On syringe needle, ground wire is connected on conductive charcoal.Apply 20kV high pressures, injection flow rate pump is 0.4ml h-1, acetic acid is obtained after collecting 4h
Stannous/polyacrylonitrile/N,N-dimethylformamide/dimethyl sulfoxide (DMSO) composite fiber thin film.
(2) composite fiber thin film obtained by step (1) is placed in tube furnace and calcines 1h in air atmosphere, calcination temperature
It it is 400 DEG C, heating rate is 5 DEG C of min-1.N,N-Dimethylformamide/dimethyl sulfoxide (DMSO) will decompose, and stannous acetate closes object quilt
It is oxidized to stannic oxide, nanometer tin based electrochemical reduction carbon dioxide catalyst, the stereoscan photograph of catalyst is prepared
As shown in Figure 1, transmission electron microscope photo is as shown in Figure 2.
(3) catalyst and 100 μ L 5%Nafion solution, 1ml ethyl alcohol 5mg steps (2) being prepared mix and surpass
Sound disperses, and 100 μ L dispersant liquid drops are then added in 1cm2Carbon paper on, at 60 DEG C dry.It is prepared and is used for electrochemical reduction
The load capacity of the electrode of carbon dioxide, catalyst is 0.5mg cm-2。
(4) electrode for preparing step (3) is as working electrode, and platinum electrode is used as to electrode, and Ag/AgCl electrodes are as ginseng
Than electrode, electrochemically reducing carbon dioxide is carried out in H bottles, electrolyte is 0.5M KHCO3, H bottles it is intermediate using Nafion membrane every
It opens.Gaseous product is quantified using gas-chromatography, nuclear magnetic resonance spectroscopy is quantitative for liquid product.
Embodiment 3
(1) 0.5g polyvinyl alcohol (PAN, Mw=9,500,0) and 0.5g stannous sulfates 10ml water is dissolved in mix with 1ml ethyl alcohol
In in bonding solvent, stirs obtain spinning solution afterwards for 24 hours at room temperature, be transferred into syringe, be placed on syringe pump, over there
One block of conductive charcoal is placed at 18cm, as electrostatic spinning reception device.High voltage power supply is connected on syringe needle, ground wire is connect
On conductive charcoal.Apply 15kV high pressures, injection flow rate pump is 0.5ml h-1, collect 4h after obtain stannous sulfate/polyvinyl alcohol/
Water/ethyl alcohol composite fiber thin film.
(2) composite fiber thin film obtained by step (1) is placed in tube furnace and calcines 5h in air atmosphere, calcination temperature
It it is 650 DEG C, heating rate is 5 DEG C of min-1.Polyvinyl alcohol/water/ethyl alcohol will decompose, volatilize, and stannous sulfate is oxidized to dioxy
Change tin, nanometer tin based electrochemical reduction carbon dioxide catalyst is prepared.
(3) catalyst and 100 μ L 5%Nafion solution, 1ml ethyl alcohol 20mg steps (2) being prepared mix and surpass
Sound disperses, and 100 μ L dispersant liquid drops are then added in 1cm2Carbon paper on, at 60 DEG C dry.It is prepared and is used for electrochemical reduction
The load capacity of the electrode of carbon dioxide, catalyst is 2mg cm-2。
Claims (10)
1. a kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst, which is characterized in that for by stannic oxide nanometer
The one-dimentional structure of pipe and stannic oxide nano wire composition, the tin dioxide nanometer tube are set in outside the stannic oxide nano wire
Portion.
2. electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst according to claim 1, which is characterized in that institute
The length for stating tin dioxide nanometer tube is 1~10 micron, draw ratio is 2~20；
The length of the stannic oxide nano wire is 1~10 micron, draw ratio is 2~50.
3. a kind of preparation method of nanometer tin-based catalyst according to claim 1 or 2, which is characterized in that steps are as follows：
(1) pink salt, high polymer are mixed with mixed solvent and obtains spinning solution, composite fiber thin film is obtained through electrostatic spinning process；
The mixed solvent is made of solvent A and solvent B, and the difference of the boiling point of solvent A and the boiling point of solvent B is 10~80 DEG C；
(2) composite fiber thin film prepared by step (1) under the conditions of oxygen-containing is subjected to high-temperature calcination, obtains the nanometer tinbase
Catalyst.
4. the preparation method of according to claim 3 nanometer of tin-based catalyst, which is characterized in that in step (1), the tin
Salt is selected from stannous chloride, stannous acetate, stannous sulfate；
The high polymer is selected from polyvinylpyrrolidone, polyacrylonitrile, polystyrene, polyvinyl alcohol, polypropylene.
5. the preparation method of according to claim 3 nanometer of tin-based catalyst, which is characterized in that in step (1), the spinning
In silk liquid, the mass fraction of pink salt is 5~20%, and the mass fraction of high polymer is 5~20%.
6. the preparation method of according to claim 5 nanometer of tin-based catalyst, which is characterized in that in step (1), the spinning
In silk liquid, the mass ratio of pink salt and high polymer is 0.1~1：1.
7. the preparation method of according to claim 3 nanometer of tin-based catalyst, which is characterized in that described mixed in step (1)
Bonding solvent be selected from ethyl alcohol/N,N-dimethylformamide, ethanol/water, water/N,N-dimethylformamide, ethyl alcohol/dimethyl sulfoxide (DMSO),
N,N-dimethylformamide/dimethyl sulfoxide (DMSO)；Water/dimethyl sulfoxide (DMSO).
The volume ratio of the in the mixed solvent, solvent A and solvent B are 0.1~10：1.
8. the preparation method of according to claim 3 nanometer of tin-based catalyst, which is characterized in that described quiet in step (1)
The technique of Electrospun is：
Voltage range is 10~20kV, and distance of the reception device apart from injection syringe needle is 10~20cm.
9. the preparation method of according to claim 3 nanometer of tin-based catalyst, which is characterized in that in step (2), the height
The temperature of temperature calcining is 350~650 DEG C, and the time is 1~5h.
10. a kind of electrochemically reducing carbon dioxide reaction electrode, including electrode holder, which is characterized in that will be such as claim 1
Or the nanometer tin-based catalyst described in 2 is carried on the electrode holder, load capacity is 0.1~10mg/cm2。
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Cited By (4)
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| CN110117794A (en) * | 2019-05-21 | 2019-08-13 | 盐城工学院 | A kind of electroreduction CO2The three Room type electrolytic cell devices and its electrolytic method of formates processed |
| CN110743594A (en) * | 2019-10-31 | 2020-02-04 | 同济大学 | Nitrogen-doped carbon-loaded tin and tin oxide nanocomposite and preparation and application thereof |
| CN111333104A (en) * | 2020-02-28 | 2020-06-26 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of nanoscale tin dioxide |
| CN113786827A (en) * | 2020-05-26 | 2021-12-14 | 上海科技大学 | Stannous oxide catalyst, electrode and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117794A (en) * | 2019-05-21 | 2019-08-13 | 盐城工学院 | A kind of electroreduction CO2The three Room type electrolytic cell devices and its electrolytic method of formates processed |
| CN110743594A (en) * | 2019-10-31 | 2020-02-04 | 同济大学 | Nitrogen-doped carbon-loaded tin and tin oxide nanocomposite and preparation and application thereof |
| CN111333104A (en) * | 2020-02-28 | 2020-06-26 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of nanoscale tin dioxide |
| CN111333104B (en) * | 2020-02-28 | 2022-09-20 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of nanoscale tin dioxide |
| CN113786827A (en) * | 2020-05-26 | 2021-12-14 | 上海科技大学 | Stannous oxide catalyst, electrode and application |
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Application publication date: 20180824 |