CN103668311B - For electro-catalysis reduction CO2to the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid - Google Patents
For electro-catalysis reduction CO2to the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid Download PDFInfo
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Abstract
The present invention relates to a kind of for electro-catalysis reduction CO2To the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid.For electro-catalysis reduction CO2To the catalysis electrode of formic acid, including the coating of glass carbon plate with the tin ash containing Lacking oxygen being coated on glass carbon plate.200 ~ 400 DEG C of vacuum heat 2 ~ 4 h of tin ash can be obtained by the described tin oxide containing Lacking oxygen.This is used for electro-catalysis reduction CO2Catalysis electrode to formic acid is applied to electro-catalysis reduction carbon dioxide, can improve its electro-catalysis reduction carbon dioxide to the speed of formic acid and current efficiency.Under same potential, the speed ratio of its reduction carbon dioxide to formic acid is untreated increases nearly 3 times, and current efficiency also improves by about one time.
Description
Technical field
The present invention relates to a kind of for electro-catalysis reduction CO2To the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid.
Background technology
Since the industrial revolution, the life mode of production of human society there occurs huge change, and demand and utilization to the energy increase day by day, and meanwhile, a large amount of consumption of fossil fuels environment and the lack of energy problem brought are the most increasingly severe.The global warming issue caused along with greenhouse effects becomes increasingly conspicuous, and carbon dioxide also receives as a kind of main greenhouse gases and pays close attention to the most widely.
Under field conditions (factors), the carbon dioxide in air can be fixed by the photosynthesis of plant, and be converted into and as the carbohydrate of energy substance, thus can complete the cyclic process of carbon, maintains the concentration of carbon dioxide in air.But it is as the carbon dioxide that the mankind are discharged in air to sharply increase, carbon dioxide cumulant in environment constantly goes up assorted, climatic deterioration is caused to aggravate, life to people causes baneful influence, the most how to imitate photosynthesis, it is other carbon-containing molecules by carbon dioxide conversion effectively, it is achieved recycling of carbon, is an arduousness and imperative challenge for us.Owing to the carbon atom in carbon dioxide is the carbon of highest oxidation state, carbon dioxide molecule is in the state of minimum energy, therefore carbon dioxide is converted into, by chemical method, the energy that other materials inevitably need to provide extra, such as luminous energy, heat energy, biomass energy etc..
Electro-catalysis reduction carbon dioxide, due to its mode efficient, simple, receive more and more attention and study, wherein problem demanding prompt solution mainly include following some: 1) reduce reaction overpotential, reduce reaction energy consumption；2) improve current utilization rate, be reduced into appointment product with promoting carbon dioxide selectivity, reduce other side reaction simultaneously；3) reaction rate is improved, the conversion ratio of carbon dioxide molecule in the quickening unit interval.In order to realize this target, people have carried out much research and exploration in this respect.At CO2Electrochemical reduction in, people are concerned with metal material mostly, and the research report of this respect is also a lot, but the critically important problem that metal material faces is its stability, and metal electrode is easily at long-time electroreduction CO2During occur decay of activity.Comparatively speaking, metal oxide is more stable in electrolytic process, based on this point, is attempted to develop high stable and has again the metal oxide of high current efficiency as catalyst simultaneously.But due to electric conductivity, alternative metal oxide catalyst is the most few.Such as, Kanan group was the most once studied by cuprous nano copper particle (the Journal of The obtained of reduction-oxidation
Electrochemical Society 158 (2011) E45-E49), its electro-catalysis reduction carbon dioxide can be made to be significantly improved to the current efficiency of carbon monoxide and formic acid；But cuprous oxide is easy under conditions of electrolysis become copper simple substance, to such an extent as to loses catalysis activity.
Tin ash is the metal oxide that a kind of comparison is special, and its electric conductivity is relatively good, and at CO2Electro-reduction process in more stable, but at present the electro-catalysis reduction carbon dioxide of report is not ideal enough to the current efficiency of formic acid.
Summary of the invention
The technical problem to be solved is to provide a kind of for electro-catalysis reduction CO2To the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
For electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: it includes glass carbon plate and the coating of the tin ash containing Lacking oxygen being coated on glass carbon plate.
By such scheme, 200 ~ 400 DEG C of vacuum heat 2 ~ 4 h of tin ash are obtained by the described tin ash containing Lacking oxygen.
By such scheme, the absolute pressure of described vacuum heat is 1 ~ 10 Pa.
By such scheme, the coating of the described tin ash containing Lacking oxygen is by ultrasonic for the tin ash Nafion solution containing Lacking oxygen mixing dispersion, then the suspension after dispersion is coated in glass carbon plate surface, and drying obtains.
By such scheme, the content of the tin ash containing Lacking oxygen in described suspension is 2 wt%-10wt%.
By such scheme, the concentration of the tin ash Nafion solution that described dispersion contains Lacking oxygen is 0.1 wt%-0.5 wt%.
For electro-catalysis reduction CO2Catalysis electrode to formic acid reduces CO in electro-catalysis2Application to formic acid.
Utilize this catalysis electrode electro-catalysis reduction carbon dioxide to the method for formic acid, it is characterised in that: it is to be divided into by PEM in the electrolytic cell of anode slot and cathode can, with above-mentioned for electro-catalysis reduction CO2Catalysis electrode to formic acid is working electrode (negative electrode), and platinized platinum is auxiliary electrode (anode), and saturated calomel electrode is reference electrode, is respectively charged into electrolyte solution, is passed through CO in cathode can in anode slot and cathode can2To saturated, then it is being passed through CO continuously2Under conditions of constant potential reduction CO2, the control of Electric potentials scope in described constant potential reduction process is-1.5 ~-1.6 V.
By such scheme, described electrolyte solution is the bicarbonate solution such as KHCO of 0.5 mol/L3、NaHCO3。
It is an advantage of the current invention that:
1, the present invention obtains the tin ash containing Lacking oxygen by tin ash carries out vacuum heat, and then the catalysis electrode prepared is applied to electro-catalysis reduction carbon dioxide, can improve its electro-catalysis reduction carbon dioxide to the speed of formic acid and current efficiency.Under same potential, the speed ratio of its reduction carbon dioxide to formic acid is untreated increases nearly 3 times, and current efficiency also improves by about one time.
2, this catalysis electrode preparation method step is simple, easy to operate, it is easy to produce.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum before and after tin ash vacuum heat.
Fig. 2 is the electron paramagnetic resonance collection of illustrative plates before and after tin ash vacuum heat.
Fig. 3 is electrode constant potential catalysis reduction carbon dioxide in the catalysis electrode of the embodiment of the present invention 1 and check experiment to during formic acid, the cumulant time history plot of formic acid.
Fig. 4 is the electrode constant potential catalysis reduction carbon dioxide in the catalysis electrode of the embodiment of the present invention 1 and check experiment to the time dependent scatter diagram of current efficiency of formic acid.
SnO in figure2(V) it is the tin oxide after vacuum heat.
Detailed description of the invention
Embodiment
1
For electro-catalysis reduction CO2Preparation to the catalysis electrode of formic acid:
Step 1: by business SnO2Carrying out vacuum heat 4h, vacuum pressure 2 Pa, treatment temperature is 200 DEG C, obtains the tin ash (SnO containing Lacking oxygen2(V)), the XRD before and after it processes is shown in that Fig. 1, electron paramagnetic resonance collection of illustrative plates are shown in Fig. 2, and by the result of Fig. 2 it can be seen that tin ash is after vacuum heat, electron paramagnetic resonance signal is higher, illustrates that its surface creates Lacking oxygen defect；
Step 2: the tin ash (SnO containing Lacking oxygen after processing2(V)) ultrasonic with the Nafion solution of 0.1 wt% mix dispersion, obtain SnO2(V) mass concentration is the suspension of 2wt%, then the suspension after dispersion is coated in glass carbon plate surface, and drying is for electro-catalysis reduction CO2Catalysis electrode to formic acid.
Utilize this catalysis electrode catalysis reduction carbon dioxide to the method for formic acid: being divided into by PEM in the electrolytic cell of anode slot and cathode can, with above-mentioned catalysis electrode as working electrode (negative electrode), platinized platinum is auxiliary electrode (anode), saturated calomel electrode is reference electrode, is respectively charged into 0.5 M KHCO in anode slot and cathode can3Solution, and in cathode can, it is passed through CO2To saturated, then it is being passed through CO continuously2Under conditions of constant potential reduction carbon dioxide, control of Electric potentials is at-1.6V.Another with business SnO2(without vacuum treated SnO2) it is raw material, use above-mentioned identical method to prepare catalysis electrode, compare test.
During electrocatalytic reaction every sampling in 12 minutes once, measure formate content therein thus to calculate the content of formic acid in solution, Fig. 3 is that the catalysis electrode constant potential catalysis reduction carbon dioxide in the embodiment of the present invention and check experiment is to the cumulant time history plot of formic acid during formic acid, electricity in combination with each corresponding time period Inner electrolysis process, calculating current efficiency, Fig. 4 is the electrode constant potential catalysis reduction carbon dioxide in the catalysis electrode of the embodiment of the present invention 1 and check experiment to the time dependent scatter diagram of current efficiency of formic acid.By Fig. 3 and Fig. 4 it can be seen that under conditions of same potential, commercial oxidation tin is after vacuum heat, and the reaction rate of reduction carbon dioxide to formic acid improves nearly 3 times, and current efficiency also improves by about one time.
Embodiment
2
For electro-catalysis reduction CO2Preparation to the catalysis electrode of formic acid:
Step 1: by SnO2Carrying out vacuum heat 3h, vacuum pressure 8 Pa, treatment temperature is 300 DEG C, obtains the tin ash (SnO containing Lacking oxygen2(V))；
Step 2: by the tin ash (SnO containing Lacking oxygen2(V)) ultrasonic with the Nafion solution of 0.3wt% mix dispersion, obtain SnO2(V) mass concentration is the suspension of 5wt%, and the suspension after dispersion is coated in glass carbon plate surface, i.e. obtains for electro-catalysis reduction CO after drying2Catalysis electrode to formic acid.
Utilize this catalysis electrode catalysis reduction carbon dioxide to the method for formic acid:
It is being divided into by PEM in the electrolytic cell of anode slot and cathode can, with above-mentioned catalysis electrode as working electrode (negative electrode), platinized platinum is auxiliary electrode (anode), and saturated calomel electrode is reference electrode, is respectively charged into 0.5 M KHCO in anode slot and cathode can3Solution, and in cathode can, it is passed through CO2To saturated, then it is being passed through CO continuously2Under conditions of constant potential reduction carbon dioxide, control of Electric potentials is at-1.5V.
After being electrolysed 1 hour, take out the concentration of liquor analysis formate, in combination with the electricity of this corresponding time period Inner electrolysis process, calculate current efficiency about 47%.
Embodiment
3
For electro-catalysis reduction CO2Preparation to the catalysis electrode of formic acid:
Step 1: by SnO2Carrying out vacuum heat 2h, vacuum pressure 10 Pa, treatment temperature is 400 DEG C, obtains the tin ash (SnO containing Lacking oxygen2(V))；
Step 2: by the tin ash (SnO containing Lacking oxygen2(V)) ultrasonic with 0.5 wt%Nafion solution mix dispersion, obtain SnO2(V) mass concentration is the suspension of 3wt%, and the suspension after dispersion is coated in glass carbon plate surface, i.e. obtains for electro-catalysis reduction CO after drying2Catalysis electrode to formic acid.
Utilize this catalysis electrode catalysis reduction carbon dioxide to the method for formic acid: being divided into by PEM in the electrolytic cell of anode slot and cathode can, with above-mentioned catalysis electrode as working electrode (negative electrode), platinized platinum is auxiliary electrode (anode), saturated calomel electrode is reference electrode, is respectively charged into 0.5 M KHCO in anode slot and cathode can3Solution, and in cathode can, it is passed through CO2To saturated, then it is being passed through CO continuously2Under conditions of constant potential reduction carbon dioxide, control of Electric potentials is at-1.55V.
After being electrolysed 1 hour, take out the concentration of liquor analysis formate, in combination with the electricity of this corresponding time period Inner electrolysis process, calculate current efficiency about 51%.
Claims (8)
1. for electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: it includes glass carbon plate and the coating of the tin ash containing Lacking oxygen being coated on glass carbon plate；200 ~ 400 DEG C of vacuum heat 2 ~ 4 h of tin ash are obtained by the described tin ash containing Lacking oxygen.
The most according to claim 1 for electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: the absolute pressure of described vacuum heat is 1 ~ 10 Pa.
The most according to claim 1 for electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: the coating of the described tin ash containing Lacking oxygen is by ultrasonic for the tin ash Nafion solution containing Lacking oxygen mixing dispersion, then the suspension after dispersion is coated in glass carbon plate surface, and drying obtains.
The most according to claim 3 for electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: the content of the tin ash containing Lacking oxygen in described suspension is 2 wt%-10 wt%.
The most according to claim 3 for electro-catalysis reduction CO2Catalysis electrode to formic acid, it is characterised in that: the concentration of the tin ash Nafion solution that described dispersion contains Lacking oxygen is 0.1 wt%-0.5 wt%.
6. described in claim 1 for electro-catalysis reduce CO2Catalysis electrode to formic acid reduces CO in electro-catalysis2Application to formic acid.
7. the catalysis electrode electro-catalysis reduction carbon dioxide described in claim 1 is to the method for formic acid, it is characterised in that: it is to be divided into by PEM in the electrolytic cell of anode slot and cathode can, reduces CO with above-mentioned for electro-catalysis2Catalysis electrode to formic acid is working electrode, and platinized platinum is auxiliary electrode, and saturated calomel electrode is reference electrode, is respectively charged into electrolyte solution in anode slot and cathode can, is passed through CO in cathode can2To saturated, then it is being passed through CO continuously2Under conditions of constant potential reduction CO2, the control of Electric potentials scope in described constant potential reduction process is-1.5 ~-1.6 V.
Catalysis electrode electro-catalysis the most according to claim 7 reduction carbon dioxide is to the method for formic acid, it is characterised in that: described electrolyte solution is the bicarbonate solution of 0.5 mol/L.
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| CN104846397B (en) * | 2015-04-21 | 2018-08-31 | 盐城工学院 | One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed |
| CN104959135B (en) * | 2015-06-29 | 2017-12-05 | 华中师范大学 | A kind of nanometer zinc catalyst and based on nanometer zinc catalyst efficient catalytic CO2The method for reducing CO |
| CN105214476B (en) * | 2015-08-21 | 2018-04-27 | 浙江工商大学 | The microorganism electrochemical reactor and method of fixed carbon dioxide in waste gas generation organic matter product while treated sewage |
| CN105776502B (en) * | 2016-01-06 | 2019-04-16 | 浙江工商大学 | A kind of metal oxide modified electrode biomembrane reduction CO2Method |
| US11788195B2 (en) | 2017-09-27 | 2023-10-17 | Sekisui Chemical Co., Ltd. | Carbon dioxide reduction device, and porous electrode |
| CN108342749B (en) * | 2018-02-01 | 2020-05-12 | 太原理工大学 | Modified SnO2Preparation method of electrode and application of electrode in photoelectrocatalysis reduction of CO2Preparation of formic acid |
| CN109675545B (en) * | 2018-12-20 | 2020-06-02 | 华中科技大学 | SnO with multilayer structurexCatalyst, method for the production and use thereof |
| CN110396700A (en) * | 2019-07-26 | 2019-11-01 | 中国科学院青岛生物能源与过程研究所 | A kind of tin oxide catalysts are in electrochemical reduction CO2Application in formic acid processed |
| CN110396701B (en) * | 2019-08-19 | 2021-10-22 | 青岛科技大学 | Electrode for preparing formic acid by efficiently electro-catalytically reducing carbon dioxide |
| CN112410811A (en) * | 2020-11-19 | 2021-02-26 | 华东师范大学 | Electrocatalysis system and application thereof in producing formic acid |
| CN114686908B (en) * | 2022-03-07 | 2023-07-25 | 华中科技大学 | Method for directly generating formic acid by high-efficiency electrocatalytic carbon dioxide reduction |
| CN115286079A (en) * | 2022-09-05 | 2022-11-04 | 重庆地质矿产研究院 | Oil-based rock debris resource utilization device and method based on electrocatalysis principle |
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