CN103205773B - A kind of electrochemical reduction CO 2the method of synthesized micromolecule alcohol compound - Google Patents
A kind of electrochemical reduction CO 2the method of synthesized micromolecule alcohol compound Download PDFInfo
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- CN103205773B CN103205773B CN201310096672.2A CN201310096672A CN103205773B CN 103205773 B CN103205773 B CN 103205773B CN 201310096672 A CN201310096672 A CN 201310096672A CN 103205773 B CN103205773 B CN 103205773B
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Abstract
The invention discloses a kind of electrochemical reduction CO
2the method of synthesized micromolecule alcohol compound, is characterized in that the method adopts that copper sheet is working electrode, the saturated calomel H type two chamber-type electrolyzer that to be reference electrode and platinum guaze be to electrode, KCl, KBr, KI or KHCO
3for supporting salts solution, at ambient pressure by CO
2many potential steps formula electrolytic reduction becomes small molecular alcohol compounds.It is simple that the present invention compared with prior art has technique; easy to operate, the atmospheric carbon dioxide of Greenhouse effect is effectively utilized, greatly reduces topsoil; having very great meaning to environment protection, is a kind of operational path having very much commercial synthesis to be worth.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, specifically a kind of many potential step methods electrochemical reduction CO
2the method of synthesized micromolecule alcohol compound.
Background technology
Closely for centuries, a large amount of uses containing carbon resource cause CO in air
2concentration constantly raises, and have impact on the climatope in the world.By electrochemical method by CO
2reduction, not only can realize the circulation of carbon, also provide a kind of method for the mankind solve amblent air temperature crisis.Ethanol is a kind of conventional chemical feedstocks, and can the energy as an alternative, is the CO with higher economic benefit
2reduzate.Copper is considered to CO always
2there is the metal electrode of higher catalytic activity.As far back as nineteen ninety, Y.Hori is at Shokubai, 32(2), just reported with copper to be that electrode reduces CO in aqueous in 75-76
2c can be obtained
2h
4, CH
4, CH
3cH
2oH, n-PrOH.2004, K.Ogura is at JournalofElectroanalyticalChemistry, 565(2), reported in 287-293: with the potassium halide solution of 3M for electrolytic solution, copper electrode is carried out anodic oxidation, obtain cuprous halide modified electrode, recycling modified copper electrode is working electrode, reduces CO in potentiostatic deposition mode
2, the current efficiency that CuCl modified copper electrode obtains ethanol is 1.9%, has no other alcohols.
At present, be that working electrode carries out constant potential or constant-current electrolysis reduction CO with copper
2main existence two shortcomings: one, the current efficiency of gained ethanol is very low; Its two, along with the prolongation of electrolysis time, the carbon that electrolytic process produces easily is adsorbed on electrode surface, makes electrode lose catalytic activity.
Summary of the invention
A kind of electrochemical reduction CO provided for the deficiencies in the prior art is provided
2the method of synthesized micromolecule alcohol compound, employing copper sheet is working electrode, saturated calomel is reference electrode and platinum guaze is H type two chamber-type electrolyzer to electrode, at ambient pressure by CO
2many potential steps formula electrolytic reduction becomes small molecular alcohol compounds, and reaction system simply, is easily controlled, CO
2as main raw material, cheap and easy to get, cost is low, free from environmental pollution, is a kind of operational path having very much commercial synthesis to be worth.
The technical scheme realizing the object of the invention is: a kind of electrochemical reduction CO
2the method of synthesized micromolecule alcohol compound, is characterized in that the method adopts many potential step methods, by CO under normal pressure
2electrolytic reduction is small molecular alcohol compounds, and concrete steps are as follows:
The preparation of a, electrolytic solution
Be KCl, KBr, KI or KHCO of 0.5M by 15ml equivalent concentration
3support that salts solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, described electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode;
B, electrolytic reaction
Under normal pressure, pass into CO to above-mentioned electrolyzer
2to saturated, then adopt the electrolysis of many potential steps formula, its turn on angle is 40 ~ 120C, and electrolysis temperature is 0 ~ 5 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0.2 ~-0.2V, and the time is 2 ~ 6s, and second step current potential is set to-1.4 ~-2.2V, and the time is 4 ~ 8s;
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, adds NaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, it is ethanol and n-propyl alcohol that cut obtains product after concentrated, described NaCl and KCl, KBr, KI or KHCO
3support that the mass ratio of salts solution is respectively 12.5:1,7.8:1,6.3:1,9.3:1.
It is simple that the present invention compared with prior art has technique, easy to operate, by CO
2be reduced into the important industrial chemicals of the small molecule alcohols such as ethanol; the atmospheric carbon dioxide of Greenhouse effect is effectively utilized; greatly reduce topsoil; be a kind of operational path having very much commercial synthesis to be worth, have important meaning to containing carbon resource alleviation that is day by day exhausted and climatope crisis.
Embodiment
By following specific embodiment, the present invention is described in further detail.
Embodiment 1
The preparation of a, electrolytic solution
Be cathode compartment and the anolyte compartment that the KCl aqueous solution of 0.5M adds H type two Room electrolyzer by 15ml concentration, electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 80C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0V, and the time is 4s, and second step current potential is set to-2.0V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, add 7gNaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, cut obtains 144.3 μ g ethanol and 22.9 μ g n-propyl alcohols after concentrated, the current efficiency of its ethanol is 4.5%, and n-propyl alcohol current efficiency is 0.82%.
Embodiment 2
The preparation of a, electrolytic solution
Be the KHCO of 0.5M by 15ml concentration
3the aqueous solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, and electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, arranges the working electrode of metal copper sheet and the reference electrode of saturated calomel in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 100C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0V, and the time is 2s, and second step current potential is set to-2.0V, and the time is 8s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, add 7gNaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, cut obtains 19.0 μ g ethanol and 4.9 μ g n-propyl alcohols after concentrated, the current efficiency of its ethanol is 0.48%, and n-propyl alcohol current efficiency is 0.14%.
Embodiment 3
The preparation of a, electrolytic solution
Be the KHCO of 0.5M by 15ml concentration
3the aqueous solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, and electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, arranges the working electrode of metal copper sheet and the reference electrode of saturated calomel in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 100C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0V, and the time is 4s, and second step current potential is set to-1.4V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, adds 7gNaCl and fully dissolve rear distillation, collect ethanol fraction respectively, cut obtains 6.7 μ g ethanol after concentrated, and the current efficiency of its ethanol is 0.17%.
Embodiment 4
The preparation of a, electrolytic solution
Be the KHCO of 0.5M by 15ml concentration
3the aqueous solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, and electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, arranges the working electrode of metal copper sheet and the reference electrode of saturated calomel in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 100C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to-0.2V, and the time is 4s, and second step current potential is set to-1.8V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, adds 7gNaCl and fully dissolve rear distillation, collect ethanol fraction respectively, cut obtains 18.7 μ g ethanol after concentrated, and the current efficiency of its ethanol is 0.47%.
Embodiment 5
The preparation of a, electrolytic solution
Be cathode compartment and the anolyte compartment that the KBr aqueous solution of 0.5M adds H type two Room electrolyzer by 15ml concentration, electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 80C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and the first step current potential is set to 0V, and the time is 4s, and second step current potential is set to-2.0V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, add 7gNaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, cut obtains 141.7 μ g ethanol and 27.7 μ g n-propyl alcohols after concentrated, the current efficiency of its ethanol is 4.4%, and n-propyl alcohol current efficiency is 1.0%.
Embodiment 6
The preparation of a, electrolytic solution
Be cathode compartment and the anolyte compartment that the KI aqueous solution of 0.5M adds H type two Room electrolyzer by 15ml concentration, electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 80C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0V, and the time is 4s, and second step current potential is set to-2.0V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, add 7gNaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, cut obtains 315.6 μ g ethanol and 26.6 μ g n-propyl alcohols after concentrated, the current efficiency of its ethanol is 9.9%, and n-propyl alcohol current efficiency is 0.96%.
Embodiment 7
The preparation of a, electrolytic solution
By the KHCO of 15ml0.5M
3the aqueous solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, electrolyzer is divided into cathode compartment and anolyte compartment by 3F cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode.
B, electrolytic reaction
Under normal pressure, in above-mentioned solution, pass into CO
2to saturated, then adopt the electrolysis of many potential steps formula, turn on angle is 120C, and electrolysis temperature is 0 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is 0V, and the time is 4s, and second step current potential is set to-2.0V, and the time is 6s.
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, add 7gNaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, cut obtains 24.6 μ g ethanol and 4.7 μ g n-propyl alcohols after concentrated, the current efficiency of its ethanol is 0.52%, and n-propyl alcohol current efficiency is 0.11%.
Just the present invention will be further described for each embodiment above, and be not used to limit patent of the present invention, and all be equivalence enforcement of the present invention, within the right that all should be contained in patent of the present invention.
Claims (1)
1. an electrochemical reduction CO
2the method of synthesized micromolecule alcohol compound, is characterized in that the method adopts many potential step methods, by CO under normal pressure
2electrolytic reduction is small molecular alcohol compounds, and concrete steps are as follows:
The preparation of a, electrolytic solution
Be KCl, KBr, KI or KHCO of 0.5M by 15ml equivalent concentration
3support that salts solution adds cathode compartment and the anolyte compartment of H type two Room electrolyzer, described electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane, the working electrode of metal copper sheet and the reference electrode of saturated calomel are set in cathode compartment, arrange in anolyte compartment platinum guaze to electrode;
B, electrolytic reaction
Under normal pressure, pass into CO to above-mentioned electrolyzer
2to saturated, then adopt the electrolysis of many potential steps formula, its turn on angle is 40 ~ 120C, and electrolysis temperature is 0 ~ 5 DEG C; The electrolysis of described many potential steps formula is the setting of two step potential, and its first step current potential is set to 0.2 ~-0.2V, and the time is 2 ~ 6s, and second step current potential is set to-1.4 ~-2.2V, and the time is 4 ~ 8s;
The distillation of c, catholyte
Cathode chamber solution after electrolysis is moved to flask, adds NaCl and fully dissolve rear distillation, collect ethanol and n-propyl alcohol cut respectively, it is ethanol and n-propyl alcohol that cut obtains product after concentrated, described NaCl and KCl, KBr, KI or KHCO
3support that the mass ratio of salts solution is respectively 12.5:1,7.8:1,6.3:1,9.3:1.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105316700B (en) * | 2014-07-29 | 2017-11-14 | 中国科学院大连化学物理研究所 | A kind of electrochemically reducing carbon dioxide reaction electrolytic cell and application |
| CN105332002B (en) * | 2015-12-13 | 2017-12-26 | 兰州大学 | A kind of method that ethanol is prepared by carbon dioxide and water |
| DE102016220297A1 (en) * | 2016-09-27 | 2018-03-29 | Siemens Aktiengesellschaft | Process and apparatus for the electrochemical utilization of carbon dioxide |
| CN111378983B (en) * | 2020-03-13 | 2021-11-05 | 大连理工大学 | CO based on electrode solution system2Method for controlling electroreduction reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959094A (en) * | 1975-03-13 | 1976-05-25 | The United States Of America As Represented By The United States Energy Research And Development Administration | Electrolytic synthesis of methanol from CO2 |
| CN101328590A (en) * | 2008-06-17 | 2008-12-24 | 昆明理工大学 | Method for converting carbon dioxide into organic compound |
| CN102190573A (en) * | 2011-03-30 | 2011-09-21 | 昆明理工大学 | Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959094A (en) * | 1975-03-13 | 1976-05-25 | The United States Of America As Represented By The United States Energy Research And Development Administration | Electrolytic synthesis of methanol from CO2 |
| CN101328590A (en) * | 2008-06-17 | 2008-12-24 | 昆明理工大学 | Method for converting carbon dioxide into organic compound |
| CN102190573A (en) * | 2011-03-30 | 2011-09-21 | 昆明理工大学 | Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 《Electrocatalytic activity of Cu electrode in electroreduction》;Jaeyoung Lee, Yongsug Tak;《Electrochimica Acta》;20010620;第46卷(第19期);3015-3022 * |
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Inventor after: Wang Huan Inventor after: Wu Jing Inventor after: Lan Yangchun Inventor after: Ding Binbin Inventor after: Zhu Hongwei Inventor after: Chi Dinghui Inventor after: Lu Jiaxing Inventor before: Wang Huan Inventor before: Wu Jing Inventor before: Lan Yangchun Inventor before: Ding Binbin Inventor before: Zhu Hongwei Inventor before: Chi Dinghui Inventor before: Lu Jiaxing |
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