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CN-116288417-B - Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction

CN116288417BCN 116288417 BCN116288417 BCN 116288417BCN-116288417-B

Abstract

The invention belongs to the technical field of electrocatalytic application, and relates to a composite catalytic electrode, in particular to an application method of a tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction, which comprises the steps of taking an FTO or platinum sheet electrode loaded with BiVO 4 as a working electrode, taking carbon paper loaded with Cu 2 O-SnO 2 composite nano particles as a counter electrode, adding prepared CO 2 saturated electrolyte solution into two sides of an H-type electrolytic cell, continuously introducing CO 2 to remove oxygen, and then carrying out carbon dioxide catalytic reduction under the condition of no illumination or illumination at the gas flow rate of 20-100 mL/min at the temperature of 20-30 ℃. According to the invention, the microspheric SnO 2 is compounded on the Cu 2 O surface of the concave octahedron, so that the electrochemical impedance of the catalyst is effectively reduced, the formation of a CO 2 RR intermediate is accelerated, the electrochemical active area of the catalyst is enhanced, and meanwhile, the anode shows stronger catalytic activity after being excited by light, and the catalyst has good application prospects in the fields of environment, energy and the like.

Inventors

  • Ding Jinrui
  • YU JIANGWEI
  • JIAN ZHIWEI
  • LIU YANG

Assignees

  • 江苏大学

Dates

Publication Date
20260512
Application Date
20221128

Claims (15)

  1. 1. An application method of a tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide is characterized in that FTO loaded with BiVO 4 is used as a working electrode, namely a photo-anode, carbon paper loaded with Cu 2 O-SnO 2 composite nano particles is used as a counter electrode, namely an electric cathode, a prepared electrolyte solution saturated by CO 2 is added to two sides of an H-type electrolytic cell, CO 2 is continuously introduced to remove oxygen, and then catalytic reduction of carbon dioxide is carried out at a gas flow rate of 20-100 mL/min at a temperature of 20-30 ℃, The preparation method of the BiVO 4 -loaded FTO comprises the following steps: A. Mixing the KI solution and Bi (NO 3 ) 3 solution, wherein the pH value is regulated to be 1-2 by using concentrated nitric acid to be A solution, the ethanol solution of p-benzoquinone is B solution, and uniformly mixing the two solutions to form a mixed solution, wherein the ratio of the KI to the Bi (NO 3 ) 3 to the mass concentration of the p-benzoquinone is 100:10:15-30, and the volume ratio of the A solution to the B solution is 5:1-3); B. Taking the mixed solution as electrolyte, adding bias voltage of-0.1V relative to Ag/AgCl, electrodepositing on an FTO substrate for 3-10 min, and then uniformly dripping a dimethyl sulfoxide (DMSO) solution of 0.2M vanadyl acetylacetonate onto the surface of the FTO substrate; C. Placing the FTO substrate into a muffle furnace, heating to 300-450 ℃ at a heating rate of 2 ℃ per minute, and keeping the temperature for 2-5 hours to obtain BiVO 4 with a worm-like structure on the FTO substrate, cooling to room temperature, immersing in a 1M NaOH solution, and washing out vanadium pentoxide generated after calcination to obtain the product; the preparation method of the carbon paper loaded with the Cu 2 O-SnO 2 composite nanoparticle catalyst comprises the steps of preparing 50mL of concave octahedral Cu 2 O ethanol solution, adding 5mL of 0.1-0.3M NaCl solution, preparing 50mL of SnCl 4 ethanol solution, enabling the molar ratio of Cu to Sn to be 10-50:1, dropwise adding the SnCl 4 ethanol solution into the concave octahedral Cu 2 O ethanol solution, reacting for 5-10 min, centrifuging, cleaning, drying at the temperature of 50 ℃ in vacuum to obtain catalyst particles, taking the carbon paper as a loading substrate, uniformly ultrasonic-coating the catalyst particles on the surface of the substrate, and drying to obtain the carbon paper.
  2. 2. The method for applying the tin dioxide doped cuprous oxide composite nano catalyst to the photoelectrocatalytic reduction of carbon dioxide according to claim 1, wherein in the step A, the ratio of the mass concentration of KI to Bi (NO 3 ) 3 to the mass concentration of p-benzoquinone) is 100:10:23.
  3. 3. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the step A, the volume ratio of the solution A to the solution B is 5:2.
  4. 4. The method for applying the tin dioxide doped cuprous oxide composite nano catalyst to the photoelectrocatalytic reduction of carbon dioxide according to claim 1, wherein in the step B, electrodeposition is carried out on an FTO substrate for 5min.
  5. 5. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the step C, the FTO substrate is placed into a muffle furnace, and the temperature is raised to 450 ℃ for 2h at a temperature raising rate of 2 ℃ per minute.
  6. 6. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that the electrolyte solution saturated by CO 2 is prepared into KHCO 3 , KOH or NaCl solution with the concentration of 0.1-0.5mol.L -1 , and the solution is placed in a dark place and is saturated by introducing CO 2 .
  7. 7. The method for applying the tin dioxide doped cuprous oxide composite nano catalyst to the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that the electrolyte solution saturated by CO 2 is prepared into KHCO 3 , KOH or NaCl solution with the concentration of 0.1 mol.L -1 , and the solution is placed in a dark place and is saturated by introducing CO 2 .
  8. 8. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide is characterized in that the working voltage of an electrolytic cell is 1.2-1.6V.
  9. 9. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide according to claim 1, wherein the preparation method of the concave octahedral Cu 2 O comprises the following steps: 1. Dissolving a copper salt aqueous solution into a mixed solution of water and oleic acid, wherein the copper salt aqueous solution is a cupric salt aqueous solution and comprises one or a combination of two of a cupric sulfate aqueous solution and a cupric acetate aqueous solution; 2. adding an alkaline solution into the solution obtained in the step one, uniformly stirring, heating and preserving heat, wherein the alkaline solution comprises one or a combination of two of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution; 3. adding a reducing agent into the solution obtained in the step two, and continuously stirring until the solution reacts to obtain a cuprous oxide crude product, wherein the reducing agent comprises one or a combination of two of ascorbic acid and sodium ascorbate; 4. and (3) washing the cuprous oxide crude product obtained in the step (III), and drying in vacuum to obtain the copper oxide crude product.
  10. 10. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the first step, the concentration of the cupric salt aqueous solution is 0.01-0.1 mol/L, and the volume is 1mL.
  11. 11. The method for applying the tin dioxide doped cuprous oxide composite nano catalyst to the photoelectrocatalytic reduction of carbon dioxide, which is characterized in that in the first step, the volume ratio of water to oleic acid is 20:1.
  12. 12. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the second step, the concentration of an alkaline aqueous solution is 0.1-lmol/L, and the volume is 1mL.
  13. 13. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the second step, the heating and heat preservation temperature is 50-60 ℃.
  14. 14. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the third step, the concentration of the reducing agent is 0.01-0.1 mol/L, and the volume is 1mL.
  15. 15. The application method of the tin dioxide doped cuprous oxide composite nano catalyst in the photoelectric catalytic reduction of carbon dioxide, which is characterized in that in the fourth step, a cuprous oxide crude product is washed by adopting an ethanol and cyclohexane mixed solvent and is washed for 2-3 times.

Description

Application method of tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction Technical Field The invention belongs to the technical field of electrocatalytic application, relates to a composite catalytic electrode, and particularly relates to an application method of a tin dioxide doped cuprous oxide composite nano catalyst in carbon dioxide photoelectrocatalytic reduction. Background In recent decades, the concentration of carbon dioxide has increased, and CO 2 reduction (CO 2 RR) has become an imperative solution. Although the electrocatalytic and photocatalytic reduction modes are relatively mature, both methods face their limitations, for example, the electrocatalytic method relies heavily on the input of electric energy, and the CO 2 conversion efficiency and the product selectivity of the photocatalytic method are still not ideal. The photoelectrocatalysis reduction method combines the advantages of electrocatalysis and photocatalysis, and provides a very promising approach for improving the conversion efficiency of CO 2 and reducing the energy input. To date, the application of photoelectrocatalysis carbon dioxide reduction using a photoanode as a working electrode has been recently disclosed. Kim et al produced higher selectivity for CO 2 -reduction at different bias voltages by preparing the 040 crystal face of BiVO 4 in a photoanode (working electrode) -photocathode system. Liu et al efficiently photoelectrocatalyze the reduction of carbon dioxide to liquid fuel by preparing a flower-sphere-shaped BiOBr photocatalyst and a platy CuO catalyst in a photoanode-photocathode (working electrode) system. BiVO 4 is a typical n-type semiconductor, and its O2 p and Bi 6s orbitals can promote the transmission of electrons from Valence Band (VB) to Conduction Band (CB), reduce band gap energy and maintain excellent stability in aqueous solution, and is an excellent photoanode material. In aqueous electrolytes, many high performance electrocatalysts often rely on the use of precious metals, and the high cost has prevented their industrial use. Copper-based electrodes have been widely studied for their non-toxicity, low cost, simple synthesis, and abundant resources. The low-cost Sn doping and modification can obviously improve the Faraday efficiency of the copper-based electrocatalyst on CO, and according to the Density Functional Theory (DFT) calculation of related documents, the existence of Sn greatly influences the adsorption capacity of Cu, so that the adsorption capacity of H is greatly reduced, and the selectivity of CO is improved. In a photoanode (working electrode) -photocathode system, a photoanode for synthesizing BiVO 4 by electrodeposition is used as a working electrode, and a CSx nano catalyst prepared by a carbon paper substrate is regulated and controlled to perform photoelectrocatalytic reduction on carbon dioxide in different electrolytes. In addition, a platinum sheet-CS 4 system and a BiVO 4-Cu2 O system are respectively designed for a control experiment. Disclosure of Invention The invention aims to disclose an application method of a tin dioxide doped cuprous oxide composite nano catalyst (Cu 2O-SnO2 is abbreviated as CSx, x=1, 2,3,4, 5) in photoelectrocatalytic reduction of carbon dioxide. The technical scheme is as follows: Bismuth nitrate, potassium iodide, p-benzoquinone, ethanol and FTO conductive glass are used as raw materials, and BiVO 4 is grown on the surface of the FTO by an electrodeposition method and calcination treatment. Copper sulfate, oleic acid, sodium hydroxide and sodium ascorbate are used as raw materials, concave octahedral Cu 2 O is prepared by stirring at constant temperature, and then sodium chloride, stannic chloride, ethanol and conductive carbon paper are used as raw materials, and CSx is prepared by stirring and precipitating. An application method of a tin dioxide doped cuprous oxide (Cu 2O-SnO2) composite nano catalyst in the photoelectrocatalytic reduction of carbon dioxide comprises the steps of taking an FTO or platinum sheet electrode loaded with BiVO 4 as a working electrode, taking carbon paper loaded with Cu 2O-SnO2 composite nano particles as a counter electrode, adding prepared CO 2 saturated electrolyte solution at two sides of an H-type electrolytic cell, continuously introducing CO 2 to remove oxygen, and then carrying out the catalytic reduction of carbon dioxide under the condition of no illumination or illumination at the gas flow rate of 20-100 mL/min at the temperature of 20-30 ℃. In the preferred embodiment of the invention, the electrolyte solution saturated by CO 2 is prepared by placing KHCO 3, KOH or NaCl solution with the concentration of 0.1-0.5mol.L -1, preferably 0.1mol.L -1 in a dark place, and introducing CO 2 to saturate the solution. The preparation method of the carbon paper loaded with the Cu 2O-SnO2 composite nanoparticle catalyst comprises the steps of preparing 50mL of co