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CN-122013208-A - Method for realizing base catalytic organic oxidation reaction in non-strong alkaline solution through local pH regulation and control

CN122013208ACN 122013208 ACN122013208 ACN 122013208ACN-122013208-A

Abstract

The invention discloses a method for realizing base catalytic organic oxidation reaction in non-strong alkaline solution through local pH regulation, which comprises the steps of taking the non-strong alkaline solution containing organic matters as electrolyte, applying alternating current to electrodes, periodically switching the polarity of the electrodes, and periodically and alternately switching the polarity of the same electrode between a cathode state and an anode state. By adopting the method provided by the invention, the pH value of the non-strong alkaline solution is not required to be regulated to be strong alkaline, and the OH ‑ generated by the electrode in the cathode state builds a strong alkaline environment on the surface of the electrode in situ, so that the alkaline catalytic organic oxidation reaction which depends on the strong alkaline environment can be still stably supported to continuously and efficiently carry out under the condition that the bulk phase is in the non-strong alkaline condition. Through regulating and controlling the alternating current period, the accurate regulation and control of the local pH value of the electrode surface can be realized, so that the base catalytic organic oxidation reaction is accurately and efficiently catalyzed.

Inventors

  • SHE GUANGWEI
  • WANG HAOJING
  • SHI WENSHENG

Assignees

  • 中国科学院理化技术研究所

Dates

Publication Date
20260512
Application Date
20251226

Claims (18)

  1. 1. A method for realizing base catalytic organic oxidation reaction in non-strong alkaline solution through local pH regulation and control is characterized by comprising the steps of taking the non-strong alkaline solution containing organic matters as electrolyte, applying alternating current to electrodes, and periodically switching the polarity of the electrodes to enable the polarity of the same electrode to be periodically and alternately switched between a cathode state and an anode state.
  2. 2. The method according to claim 1, comprising an alkaline pretreatment step of immersing the electrode in a strongly alkaline solution containing the organic matter, before the alternating current is applied to the electrode.
  3. 3. The method according to claim 2, wherein the electrode is immersed in the strongly alkaline solution containing the organic matter for a period of 2 to 60 seconds.
  4. 4. The method of claim 1, wherein the electrode is selected from any one of a platinum electrode, a platinum rhodium alloy electrode, a titanium felt coated platinum electrode, a nickel foam electrode, and a titanium electrode.
  5. 5. The method of claim 1, wherein the waveform of the alternating current is selected from a square wave, a sine wave, a triangle wave, or a sawtooth wave.
  6. 6. The method of claim 1, wherein the waveform of the alternating current is selected from square waves.
  7. 7. The method of claim 1, wherein the alternating current has a voltage of 1-380V.
  8. 8. The method of claim 7, wherein the alternating current has a voltage of 1.2-1.8V.
  9. 9. The method according to claim 1, wherein the period of the alternating current is 0.1-60s.
  10. 10. The method of claim 1, wherein the electrolyte is at a temperature of 5-95 ℃.
  11. 11. The method of claim 1, wherein the non-strongly alkaline solution has a pH < 8.5.
  12. 12. The method according to claim 1, wherein the non-strongly alkaline solution is selected from any one or more of natural seawater, river water, tap water.
  13. 13. The method of claim 1, wherein the base catalyzed organic oxidation is an organic oxidation that is dependent on a strongly alkaline environment.
  14. 14. The method of claim 13, wherein the base-catalyzed organic oxidation is selected from any of ethylene glycol oxidation, glycerol oxidation, urea oxidation, and hydrazine oxidation.
  15. 15. The method according to claim 2, characterized in that the strongly basic solution used for the alkaline pretreatment step has a pH >11 and the strongly basic solution has 0.1-10mol/L of the organic matter dissolved therein.
  16. 16. The method according to claim 14, wherein the strong alkaline solution in the alkaline pretreatment step is alkaline seawater in which 2mol/L ethylene glycol is dissolved.
  17. 17. The method of claim 1, wherein the electrolyte is natural seawater containing 2mol/L ethylene glycol.
  18. 18. The method of any one of claims 1-17, wherein the electrolyte is the non-strongly alkaline solution containing 0.1-10mol/L of the organic matter.

Description

Method for realizing base catalytic organic oxidation reaction in non-strong alkaline solution through local pH regulation and control Technical Field The invention belongs to the field of electrocatalysis, and particularly relates to a method for performing an electrocatalytic base-catalyzed organic oxidation reaction in a non-strong alkaline solution. Background The excessive dependence of fossil fuels causes the problems of energy shortage and environmental pollution to be increasingly serious, and hydrogen energy is an important choice for replacing fossil fuels as a clean energy carrier. Although clean and efficient, the anode Oxygen Evolution Reaction (OER) has slow dynamics, high overpotential and limited economic benefit, and severely restricts the development of the technology. In order to improve the energy efficiency and economy of electrolytic hydrogen production, researchers have widely explored to replace OER with more economically valuable anode reactions. Among them, organic oxidation reactions such as Ethylene Glycol Oxidation (EGOR), urea Oxidation (UOR), hydrazine oxidation (HzOR), etc., show significant advantages. From the thermodynamic aspect, the theoretical potential of EGOR is 0.065V, the theoretical potential of UOR is 0.37V, the theoretical potential of HzOR is lower, compared with OER, the reaction can greatly reduce the actual working voltage during electrolysis and reduce the electric energy consumption, from the resource utilization aspect, EGOR can be directionally converted into glycolic acid (raw materials of biodegradable materials, the market unit price is about 1.8 ten thousand yuan/ton), glyoxylic acid (medical intermediate, unit price is more than 5 ten thousand yuan/ton), hydrazine in industrial wastewater can be converted into harmless N 2 through hydrazine oxidation, the organic matter oxidation reaction is utilized to replace OER, the efficient coupling of hydrogen energy production and high-value chemical electrosynthesis can be realized, a cooperative solution is provided for clean energy conversion and pollution control, and the environment and economic dual value is provided for the electrolytic hydrogen production technology. However, such organic oxidation reactions are generally carried out efficiently and stably in a strongly alkaline environment. In actual operation, the strong alkaline condition not only increases the cost of the alkali raw material and the supplementing link, but also brings the problems of equipment corrosion, operation safety risk, waste liquid treatment and the like. Thus, there is a need to develop new technologies for electrocatalytic organic oxidation that can operate efficiently and stably under non-strongly alkaline conditions. The realization of the aim can obviously simplify the electrolytic process, reduce the maintenance cost of materials and equipment, improve the process safety and the environmental compatibility, and has important scientific significance and engineering application value for promoting the sustainable development of the green hydrogen production and organic electric synthesis technology. Disclosure of Invention In order to solve at least one or more of the above-mentioned technical problems, the present invention provides a method for implementing a base-catalyzed organic oxidation reaction in a non-strong alkaline solution through local pH adjustment, comprising the steps of applying alternating current to an electrode by using the non-strong alkaline solution containing an organic substance as an electrolyte, and periodically switching the polarity of the electrode, so that the polarity of the same electrode is periodically and alternately switched between a cathode state and an anode state. According to one embodiment of the invention, the electrode comprises a pretreatment step of immersing the electrode in a strongly alkaline solution containing organic matter, prior to applying an alternating current to the electrode. According to one embodiment of the invention, the electrodes are immersed in the strongly alkaline solution containing the organic matter for a period of 2 to 60 seconds. According to one embodiment of the invention, the electrode is selected from any one of a platinum electrode, a platinum rhodium alloy electrode, a titanium felt-coated platinum electrode, a nickel foam electrode, and a titanium electrode. Preferably, the electrode is selected to be one that does not react in the electrolyte. According to one embodiment of the invention, the waveform of the alternating current is selected from square waves, sine waves, triangular waves or saw tooth waves. According to one embodiment of the invention, the waveform of the alternating current is selected from square waves. According to one embodiment of the invention, the alternating current has a voltage of 1-380V. According to one embodiment of the invention, the alternating current has a voltage of 1.2-1.8V. According to one embodiment