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Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide

A carbon dioxide, electrochemical technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of slow cathode reaction, accelerated hydrogen evolution reaction, reduced electrocatalytic activity, etc., and achieve improved electrocatalytic activity. , The effect of long-term stability improvement and strong ability

Inactive Publication Date: 2011-09-21
KUNMING UNIV OF SCI & TECH
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Problems solved by technology

[0004] However, the existing technology of producing formic acid by electrocatalytic reduction of carbon dioxide in aqueous solution has the following problems: first, carbon dioxide is a non-polar molecule, and its solubility in aqueous solution is very small, only 0.033mol / L in the standard state, causing the cathode reaction speed to be too high. Second, in the electroreduction of carbon dioxide in an aqueous solution, in order to improve the conductivity of the electrolyte, it is necessary to add an inorganic supporting electrolyte to the electrolyte, thus inevitably bringing some inorganic impurities into the electrolyte, some of which The electrodeposition reaction occurs on the surface of the cathode, forming surface active sites with low hydrogen evolution overpotential, which leads to the acceleration of the hydrogen evolution reaction, and also reduces the electrocatalytic activity of the electrode material for the carbon dioxide electroreduction reaction.

Method used

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  • Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide
  • Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide
  • Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide

Examples

Experimental program
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Effect test

Embodiment 1

[0028] Embodiment 1: as attached figure 1 As shown, the electrolytic cell is divided into a cathode chamber and an anode chamber by a perfluorosulfonic acid type proton exchange membrane, an In electrode is used as a cathode, a graphite electrode is used as an anode, and carbon dioxide is converted into formic acid through an electroreduction reaction. The specific process is as follows:

[0029] Step 1. Dissolve 1-butyl-3-methylimidazolium trifluoromethanesulfonic acid ionic liquid in dihydrogen disulfide with a water content of 15% (mass percentage) at room temperature at a liquid / dose volume ratio of 1:4. In methyl sulfoxide, an organic solvent / ionic liquid / water mixed solution is obtained. The mixed solution is transported to the gas absorption tower for dissolving and absorbing carbon dioxide until the concentration of carbon dioxide reaches 0.05 mol / L, injecting the above solution dissolved in carbon dioxide into the cathode chamber as the cathode chamber electrolyte; a...

Embodiment 2

[0032] Embodiment 2: as attached figure 1 As shown, the electrolytic cell is divided into a cathode chamber and an anode chamber by a perfluorosulfonic acid proton exchange membrane, a Pb electrode is used as a cathode, a glassy carbon electrode is used as an anode, and carbon dioxide is converted into formic acid through an electroreduction reaction. The specific process is as follows:

[0033] Step 1: Dissolve 1-butylpyridine trifluoromethanesulfonate ionic liquid in methanol with a water content of 10% (mass percentage) at a liquid / dose volume ratio of 1:6 at room temperature to obtain an organic solvent / ionic liquid / water mixed solution, and then transport the mixed solution to the gas absorption tower, dissolve and absorb carbon dioxide until the carbon dioxide concentration reaches 0.083 mol / L, inject the above solution dissolved in carbon dioxide into the cathode chamber, and use it as the cathode chamber Electrolyte; At the same time, inject 2mol / L sodium bisulfate a...

Embodiment 3

[0036] Embodiment 3: as attached figure 1 As shown, the electrolytic cell is divided into a cathode chamber and an anode chamber by a perfluorosulfonic acid proton exchange membrane, a Sn electrode is used as a cathode, and an IrO 2 ·Ta 2 o 5 The coated titanium electrode serves as the anode, which converts carbon dioxide into formic acid through an electroreduction reaction. The specific process is as follows:

[0037] Step 1, at room temperature, according to the liquid / dose volume ratio of 1:1, 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide ionic liquid is dissolved in water content rate 5% (mass percentage ) in a mixed organic solvent of dimethyl sulfoxide / propylene carbonate (the volume ratio of dimethyl sulfoxide to propylene carbonate is 1:1) to obtain a mixed solution of organic solvent / ionic liquid / water, which is sent to the gas In the absorption tower, after dissolving and absorbing carbon dioxide until the concentration of carbon dioxide reaches 0.69 ...

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Abstract

The invention relates to a method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide, and belongs to the technical field of carbon dioxide recycling. In the method, a proton exchange membrane separates an electrolytic tank into a cathode chamber and an anode chamber, organic solvent / ionic liquid / water mixed solution in which a large amount of carbon dioxide is dissolved is injected into the cathode chamber, and aqueous solution containing supporting electrolyte is injected into the anode chamber; and after an electrolysis power supply is connected, the carbon dioxide undergoes electroreduction reaction on the cathode to form the formic acid. By the method, the organic solvent / ionic liquid / water mixed solution with the advantages of good conductivity, low viscosity, high capacity of dissolving the carbon dioxide, wide electrochemical window, and low use cost can be obtained, and when the carbon dioxide is electrically reduced in the mixed solution, the current density in the electroreduction reaction of the carbon dioxide can be improved and the electrocatalytic activity and long-time stability of a cathode material are improved.

Description

technical field [0001] The invention relates to a method for preparing formic acid by electrochemically catalytically reducing carbon dioxide, which belongs to the technical field of resource utilization of carbon dioxide. Background technique [0002] Carbon dioxide is the main component that causes the greenhouse gas effect, and it is also an important resource. Converting carbon dioxide into other chemical raw materials and reducing the use of fossil fuels is an important technical way to reduce carbon dioxide emissions, and it is also a practical problem that industries with high carbon dioxide emissions such as thermoelectricity, steel, and cement urgently need to solve. Vigorously researching and developing new technologies for carbon dioxide resource transformation can promote the rapid development of emerging industries for carbon dioxide resource utilization. [0003] Formic acid is an important basic chemical raw material, widely used in medicine, dyes, leather an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C53/02C07C51/00
CPCY02P20/54
Inventor 施锦张正延胡玉琪周忠仁华一新
Owner KUNMING UNIV OF SCI & TECH
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