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CN-121992430-A - S-doped CoV-LDH electrode material and preparation method and application thereof

CN121992430ACN 121992430 ACN121992430 ACN 121992430ACN-121992430-A

Abstract

The invention belongs to the technical field of electrocatalytic materials and biomass energy conversion, and particularly relates to an S-doped CoV-LDH electrode material, and a preparation method and application thereof. An S-doped CoV-LDH electrode material comprises a conductive substrate and an S-doped CoV-LDH active layer grown on the surface of the conductive substrate in situ, wherein S element is doped in a lattice of the CoV-LDH and partially replaces lattice oxygen in the S-doped CoV-LDH active layer. The material induces lattice distortion through S anion doping, effectively regulates and controls the electron structure of CoV-LDH, balances competitive adsorption of reaction substrates, thereby remarkably improving the activity, selectivity and stability of the electrocatalytic oxidation of HMF and successfully realizing the oxidation coupling hydrogen production of HMF with low energy consumption.

Inventors

  • WANG HONGMEI
  • ZHOU LI
  • GUO LIPING
  • ZHANG SUPING
  • GU QIQI
  • Xiao Qiaoyi
  • LIAN YUAN

Assignees

  • 嘉兴大学

Dates

Publication Date
20260508
Application Date
20260206

Claims (10)

  1. 1. An S-doped CoV-LDH electrode material, characterized in that the electrode material comprises a conductive substrate and an S-doped CoV-LDH active layer grown in situ on the surface of the conductive substrate; In the S-doped CoV-LDH active layer, S element is doped in a lattice of the CoV-LDH and partially replaces lattice oxygen.
  2. 2. The S-doped CoV-LDH electrode material of claim 1, wherein said S-doped CoV-LDH active layer has a multi-stage flower-like microsphere structure assembled from nanoplatelets and uniformly distributed on the backbone of said electrically conductive substrate.
  3. 3. The S-doped CoV-LDH electrode material of claim 1, wherein said electrically conductive substrate is nickel foam and wherein said S-doped CoV-LDH active layer has a molar ratio of Co element to V element of from 4:3 to 7:0.
  4. 4. The S-doped CoV-LDH electrode material of claim 2, wherein the molar ratio of Co element to V element is from 5:2 to 6:1.
  5. 5. A method of preparing an S-doped CoV-LDH electrode material according to any one of claims 1 to 4, comprising the steps of: Step1, dissolving a cobalt source, a vanadium source, urea and a sulfur source in water to obtain a mixed precursor solution; Step2, placing the pretreated conductive substrate in the mixed precursor solution; Step 3, carrying out hydrothermal reaction on the system obtained in the step 2 under a sealing condition to enable S-doped CoV-LDH to grow on the conductive substrate in situ; and 4, after the reaction is finished, taking out the conductive substrate, washing and drying to obtain the S-doped CoV-LDH electrode material.
  6. 6. The method according to claim 5, wherein the cobalt source is cobalt nitrate hexahydrate, the vanadium source is vanadium chloride, the sulfur source is thiourea, the concentration of the cobalt source is 0.01 to 0.1M, the concentration of the vanadium source is 0.01 to 0.05M, the concentration of urea is 0.1 to 0.5M, and the concentration of the sulfur source is 0.01 to 0.05M in the mixed precursor solution.
  7. 7. The preparation method according to claim 5, wherein the hydrothermal reaction is carried out at a temperature of 100-140 ℃ for a reaction time of 8-16 hours.
  8. 8. The method of claim 5, wherein the concentration of the sulfur source in the mixed precursor solution is 0.0375M.
  9. 9. Use of an S-doped CoV-LDH electrode material according to any one of claims 1 to 4 for electrocatalytic 5-hydroxymethylfurfural oxidation.
  10. 10. The use according to claim 9, wherein the use is in an alkaline electrolyte to anodically oxidize 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid with the S-doped CoV-LDH electrode material, while coupling a hydrogen evolution reaction at the cathode.

Description

S-doped CoV-LDH electrode material and preparation method and application thereof Technical Field The invention belongs to the technical field of electrocatalytic materials and biomass energy conversion, and particularly relates to an S-doped CoV-LDH electrode material and a preparation method thereof, and application of the material in electrocatalytic 5-Hydroxymethylfurfural (HMF) oxidative coupling hydrogen evolution reaction. Background With the increasing exhaustion of fossil fuel resources, the development of renewable energy and high value-added chemicals has become a global focus of attention. Biomass resources, an important alternative energy source, can be converted into a variety of fine chemicals. Among them, 5-Hydroxymethylfurfural (HMF) is a key biomass platform molecule that can be selectively oxidized to produce 2, 5-furandicarboxylic acid (FDCA) with high added value. FDCA, similar in structure to petroleum-based terephthalic acid (PTA), is considered an important precursor for the preparation of green biodegradable plastics. The conventional HMF oxidation method generally requires high temperature and high pressure conditions, and uses a noble metal catalyst, which is costly and environmentally-friendly. In contrast, electrocatalytic oxidation HMF (HMFOR) has the advantages of mild reaction conditions, strong controllability and the like. Particularly, the anode HMFOR and the cathode are coupled for Hydrogen Evolution Reaction (HER), so that high-value FDCA can be produced, clean hydrogen energy can be produced at the cathode at the same time, and the energy utilization efficiency is remarkably improved. Among the numerous electrocatalysts, layered Double Hydroxides (LDHs) are of great interest due to their unique layered structure and tunable metal composition. However, pure LDH materials often suffer from poor conductivity, insufficient active site exposure, and the like. More importantly, the reaction involves the synergistic effect of the organic molecule with OH - when HMFOR is carried out in an alkaline medium. The HMF molecules and OH - have strong competitive adsorption on the catalyst surface, which can occupy active sites to block HMF adsorption if OH - is too strongly adsorbed, and can lead to catalyst poisoning or slow reaction kinetics if HMF is too strongly adsorbed. Therefore, how to balance the adsorption behavior of HMF and OH - on the catalyst surface, and simultaneously improve the intrinsic conductivity and active site density of the material is a major technical bottleneck faced by developing efficient HMFOR electrocatalyst at present. The existing modification strategies such as cation doping have certain effects, but have limited regulation and control capability on electronic structures. Although anion doping (such as S, se and the like) is considered to be effective in regulating an electronic structure, researches on precisely constructing an S-doped CoV-LDH system by a one-step hydrothermal method and utilizing the lattice distortion effect thereof to solve the problem of competitive adsorption and realize efficient HMFOR coupling of HER are recently reported. Disclosure of Invention Aiming at the problems in the prior art, the invention aims to provide an S-doped CoV-LDH electrode material, which effectively regulates and controls the electronic structure of CoV-LDH by inducing lattice distortion through S anion doping, balances competitive adsorption of reaction substrates, thereby remarkably improving the activity, selectivity and stability of the electrocatalytic oxidation of HMF and successfully realizing the low-energy-consumption HMF oxidation coupling hydrogen production. The technical scheme adopted for solving the technical problems is as follows: An S-doped CoV-LDH electrode material comprises a conductive substrate and an S-doped CoV-LDH active layer grown on the surface of the conductive substrate in situ, wherein in the S-doped CoV-LDH active layer, S element is doped in a lattice of the CoV-LDH and partially replaces lattice oxygen to form Co-S bonds. Preferably, the S-doped CoV-LDH active layer has a multi-stage flower-like microsphere structure, wherein the multi-stage flower-like microsphere is assembled from nanoplatelets and is uniformly distributed on the skeleton of the conductive substrate. Preferably, the conductive substrate is foam nickel, and the molar ratio of Co element to V element in the S-doped CoV-LDH active layer is 4:3 to 7:0. Preferably, the molar ratio of Co element to V element is 5:2 to 6:1. In the present invention, the X-ray diffraction pattern of the S-doped CoV-LDH electrode material has characteristic diffraction peaks in the vicinity of 2 Theta at 11.6 °, 23.4 °, 34.1 °, 38.7 °, 60.5 °, and the characteristic diffraction peaks are shifted to a high angle compared to undoped CoV-LDH. A method of preparing the S-doped CoV-LDH electrode material of the invention, the method comprising the steps of: Step1, dissolving a cob