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CN-121976204-A - Method for paired electrosynthesis of biomass by using bifunctional electrocatalyst

CN121976204ACN 121976204 ACN121976204 ACN 121976204ACN-121976204-A

Abstract

The invention discloses a method for paired electrosynthesis of biomass by utilizing a bifunctional electrocatalyst, and belongs to the technical field of electrocatalysis and biomass conversion. The method adopts independent anode and cathode channels, a bifunctional electrocatalyst is used as anode and cathode, biomass oxidation and reduction reactions are carried out in electrolyte at the same time, the electrocatalyst is M 0 M x O y /foam metal M which is metal atom/metal cation coexistence and forms a stable interface structure, M is any one of ferronickel mixture, copper, nickel or iron, and x and y are coordination numbers of metal and oxygen in metal oxide respectively. According to the invention, the metal oxide layer is formed on the surface of the foam metal in a self-assembly way, and the heterogeneous interface of metal atoms/metal cations is constructed through electrochemical partial reduction, so that high activity and high stability are realized. The invention utilizes the property of simultaneously producing hydrogen and oxygen by the anode and the cathode of the electrolytic cell to perform paired electrosynthesis on the same substrate.

Inventors

  • XU JUNMING
  • Lv Shenjie
  • WANG RUIZHEN
  • XIA HAIHONG
  • WANG KUI
  • JIANG JIANCHUN

Assignees

  • 中国林业科学研究院林产化学工业研究所

Dates

Publication Date
20260505
Application Date
20251229

Claims (10)

  1. 1. A method for paired electrosynthesis of biomass by utilizing a bifunctional electrocatalyst is characterized by adopting independent anode and cathode channels, taking the bifunctional electrocatalyst as anode and cathode, and simultaneously carrying out biomass oxidation and reduction reactions in electrolyte, wherein the electrocatalyst is M 0 M x O y /foam metal M which is a metal atom/metal cation and coexists to form a stable interface structure, M is any one of nickel-iron mixture, copper, nickel or iron, and x and y are coordination numbers of metal and oxygen in metal oxide respectively.
  2. 2. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 1, wherein the biomass is furfural or 5-hydroxymethylfurfural.
  3. 3. The method for paired electrosynthesis of biomass using a dual function electrocatalyst according to claim 1, wherein the dual function electrocatalyst is any one of CuCu 2 O/CF、FeFe 3 O 4 /FF, nio/NF, or nife@nto/NTF.
  4. 4. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst of claim 1, wherein the catholyte is 1.0M koh+50 mM biomass, the anolyte is 1.0M koh+10 mM biomass, and the two electrodes are separated by a Nafion 117 membrane.
  5. 5. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 1, wherein in an H-type electrolyzer, the cathodic potential is 0.00 to-0.25V vs. rhe and the anodic potential is 1.45~1.70V vs.RHE.
  6. 6. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 1, wherein the system is thermostated at 25 ℃ in a two-channel fluidized bed, the two cells are simultaneously cycled at 200 mA cm -2 using a current and at 1.2 mL min -1 flow rate by a two-channel peristaltic pump.
  7. 7. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 1, wherein the preparation of the bifunctional electrocatalyst comprises the steps of: (1) Etching foam metal, sequentially ultrasonically cleaning in ethanol and ultrapure water after the treatment is finished, calcining, cooling, flushing with ultrapure water and drying; (2) And (3) reducing the product obtained in the step (1) in a three-electrode electrolytic tank containing KOH solution to obtain the bifunctional electrocatalyst.
  8. 8. The method for paired electrosynthesis of biomass using bifunctional electrocatalyst according to claim 7, wherein in step (1), metal foam is cut to 1.0 cm ×2.5: 2.5 cm, and the thickness is 1mm, and etched for 30 minutes using 3M HCl, and ultrasonically cleaned in ethanol and ultrapure water, respectively, for 30min.
  9. 9. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 7, wherein step (1) is performed by heating at a rate of 5 ℃ min -1 in an air atmosphere and calcining at 250 to 350 ℃ for 2 hours.
  10. 10. The method for paired electrosynthesis of biomass using a bifunctional electrocatalyst according to claim 7, wherein in step (2), the biomass is reduced at a current density of 0.5 to 2.5 a·cm -2 for 15 minutes, and the reduction temperature is controlled to 25 ℃.

Description

Method for paired electrosynthesis of biomass by using bifunctional electrocatalyst Technical Field The invention belongs to the technical field of electrocatalysis and biomass conversion, and particularly relates to a method for paired electrosynthesis of biomass by utilizing a bifunctional electrocatalyst, which is used for simultaneous oxidation and reduction reactions of furfural and other aldehyde-containing biomass molecules. Background Furfural (Furfural) is a key platform compound derived from lignocellulosic biomass and is an important raw material for preparing furfuryl alcohol, furoic acid, furan resin and biofuel. Traditional furfural conversion is mainly realized by thermocatalytic hydrogenation or oxidation, but the reaction is usually carried out under the conditions of high temperature (150-200 ℃) and high pressure (2-5 MPa ℃) and depends on noble metal catalysts (such as Pd, pt and the like), so that the energy consumption is high, the cost is high and potential safety hazards exist. In addition, side reactions in the thermocatalytic process are prone to over-reduction or over-oxidation, resulting in reduced selectivity of the target product. In recent years, electrochemical catalytic technology has become an important research direction for biomass molecule conversion due to the advantage that electron and proton transfer can be precisely controlled under mild conditions. By applying an external potential, the selective hydrogenation or oxidation of furfural molecules can be realized. However, most of the current research focuses on monopolar reactions, namely cathodic furfural reduction reactions (furfural electroreduction reaction, FFER) or anodic furfural oxidation reactions (furfural oxidation reaction, FFOR), while the other pole is mainly Hydrogen Evolution Reactions (HER) or Oxygen Evolution Reactions (OER), which result in a lower energy utilization of the system. In addition, although the H-type electrolytic cell can separate cathode and anode reactions, in a traditional static reaction system, the substrate diffusion is limited, the bubble accumulation is serious, and the local concentration gradient is large, so that the reaction efficiency is low. The fluidized bed electrolysis system can obviously improve the mass transfer rate and the gas release rate of a reaction interface by continuously circulating electrolyte, and ensures the full utilization of active sites on the surface of an electrode. However, the combination of this system with metal-based bifunctional catalysts for oxidation-reduction paired electrosynthesis of furfural and other biomass molecules has not been reported publicly. In summary, there is an urgent need for an electrocatalytic system capable of simultaneously implementing cathodic reduction and anodic oxidation of furfural or pentahydroxymethyl furfural under mild conditions, and having both high energy efficiency and high stability. Disclosure of Invention The invention solves the technical problem of providing a method for paired electrosynthesis of biomass by utilizing a bifunctional electrocatalyst, which realizes high-energy-efficiency electrosynthesis of biomass by utilizing a electrocatalyst with stable structure, high conductivity and excellent bifunctional activity. The technical scheme adopted by the invention is as follows in order to solve the technical problems: A method for paired electrosynthesis of biomass by utilizing a bifunctional electrocatalyst adopts independent anode and cathode channels, takes the bifunctional electrocatalyst as anode and cathode, and simultaneously carries out biomass oxidation and reduction reaction in electrolyte, wherein the electrocatalyst is M 0MxOy/foam metal M which is a metal atom/metal cation and coexists to form a stable interface structure, M is any one of nickel-iron mixture, copper, nickel or iron, and x and y are coordination numbers of metal and oxygen in metal oxide respectively. The catalyst takes metal foam as a three-dimensional conductive framework, a metal oxide nano sheet layer is formed on the surface of the three-dimensional conductive framework through air calcination, and then the metal oxide nano sheet layer is converted into metal atoms through an electrochemical reduction part, so that a metal atom/metal cation synergistic structure is formed. The structure provides excellent electron transport capability and maintains high surface active site density. The method for paired electrosynthesis of biomass by utilizing the bifunctional electrocatalyst comprises the step of preparing the biomass which is furfural or 5-hydroxymethylfurfural. The method for paired electrosynthesis of biomass by utilizing the bifunctional electrocatalyst is characterized in that the bifunctional electrocatalyst is any one of CuCu 2O/CF、FeFe3O4/FF, niNiO/NF or NiFe@NTO/NTF. According to the method for paired electrosynthesis of biomass by utilizing the bifunctional electrocatalyst, the catholyte is 1.0M KOH+50