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CN-122013231-A - WC@Cu/M composite material and preparation and application thereof

CN122013231ACN 122013231 ACN122013231 ACN 122013231ACN-122013231-A

Abstract

The invention discloses a WC@Cu/M composite material and preparation and application thereof. The preparation method of the WC@Cu/M composite material comprises the following steps of (1) obtaining nanoscale WC@Cu particles, (2) placing the nanoscale WC@Cu particles in a muffle furnace, oxidizing the nano-scale WC@Cu particles at 280-300 ℃ for 20-40min in an air atmosphere to obtain oxidized WC@Cu particles, and (3) placing the oxidized WC@Cu particles in a solution containing an M compound for displacement reaction, then carrying out solid-liquid separation and drying to obtain the WC@Cu/M composite material. The invention provides application of WC@Cu/M serving as an electrocatalyst in glycerol electrooxidation synergistic hydrogen production. The WC@Cu/M composite material obtained by the method introduces a copper oxide component, so that the catalytic activity of the WC@Cu/M composite material in the glycerol electrooxidation synergistic hydrogen production can be improved.

Inventors

  • CHEN ZHAOYANG
  • SHAO JIAHAO
  • ZHENG JIAJUN
  • CHU YOUQUN

Assignees

  • 浙江工业大学

Dates

Publication Date
20260512
Application Date
20251105

Claims (10)

  1. 1. A preparation method of a WC@Cu/M composite material is characterized by comprising the following steps of: (1) Obtaining nano WC@Cu particles, wherein the weight ratio of Cu to W is 1:3-10, and the particles are of a core-shell structure with WC as a core and Cu as a shell; (2) The nano WC@Cu particles are placed in a muffle furnace and oxidized for 20-40min at 280-300 ℃ in air, so that oxidized WC@Cu particles are obtained; (3) And (3) placing oxidized WC@Cu particles into a solution containing an M compound for substitution reaction, enabling the mass ratio of M on substitution to the oxidized WC@Cu particles to be 1-10:100, performing solid-liquid separation, and drying to obtain the WC@Cu/M composite material.
  2. 2. The method of claim 1, wherein M is platinum or palladium.
  3. 3. The method of claim 1 or 2, wherein the weight ratio of Cu to W in the nano-sized WC@Cu particles is 1:3-5.
  4. 4. The method of claim 3, wherein the weight ratio of Cu to W in the nano-sized WC@Cu particles is 1:4.
  5. 5. The process according to claim 1 or 2, wherein in step (2), the oxidation temperature is 285 to 295℃and the oxidation time is 25 to 35 min.
  6. 6. The process according to claim 5, wherein in the step (2), the oxidation temperature is 290℃and the oxidation time is 30min.
  7. 7. The method of claim 2, wherein in step (3), the M-containing compound is palladium chloride or chloroplatinic acid.
  8. 8. The method according to claim 1 or 2, wherein in the step (3), the mass ratio of M on the substitution to WC@Cu particles after oxidation is 4-6:100.
  9. 9. A wc@cu/M composite material prepared according to the preparation method of any one of claims 1-8.
  10. 10. The use of wc@cu/M as defined in claim 9 as an electrocatalyst for the electro-oxidation co-production of hydrogen from glycerol.

Description

WC@Cu/M composite material and preparation and application thereof Technical Field The invention relates to a WC@Cu/M composite material, a preparation method thereof and application of the WC@Cu/M composite material serving as an electrocatalyst in glycerol electrooxidation synergistic hydrogen production. Background Biomass-derived Glycerol (GLY) is a residual and low cost byproduct of biodiesel, soap production and processing plants, and its oxidation reaction (GOR) is an ideal alternative to Oxygen Evolution Reaction (OER) because its theoretical redox potential is lower than 0.003V, lower than RHE, compared to OER. Meanwhile, as an excellent biological platform molecule, the protein can be converted into a series of value-added C 3-C1 products. The activity and selectivity of GOR is largely dependent on the intrinsic properties of the electrocatalyst. Noble metal-based electrocatalysts have been widely reported for GOR due to their good corrosion resistance and low initiation potential through alloying, heteroatom doping and nanostructure engineering. However, this process involves a complex 12 electron transfer path, with three bottlenecks of high c—c bond cleavage energy barrier, intermediate CO poisoning active sites, and catalyst alkaline dissolution. Although the traditional Pt/C catalyst has certain activity, the selectivity to C-C bonds is poor, the noble metal consumption is as high as more than 20 wt%, and the industrial application is severely restricted. Tungsten carbide (WC) has been widely studied as a substitute for platinum group noble metal catalysts because of its platinum-like electronic structure, high conductivity, and excellent chemical stability. WC presents significant cost advantages and environmental resistance, especially in electrocatalytic reactions such as Hydrogen Evolution (HER), oxygen reduction (ORR), etc. However, the conventional WC powder has a limited specific surface area, a low density of surface active sites, and a smooth surface causes insufficient mass transfer efficiency of reactants, severely restricting catalytic activity thereof. Tungsten carbide-copper (WC-Cu) composite matrix becomes an ideal substitute carrier due to the excellent conductivity (5.96×10 7 S/m) of the fused WC-like platinum electronic properties (d-band center-2.8 eV) and copper. However, the surface roughness of the existing WC-Cu material is less than 50 nm, the specific surface area is generally lower than 15m < 2 >/g, and the dense copper layer more obstructs reactants from contacting the WC active sites of the bottom layer, so that the intrinsic activity is difficult to release. The paper [Zhao-Yang Chen, Chun-An Ma, You-Qun Chu, Jia-Mei Jin, Xiao Lin, Christopher Hardacreb and Wen-Feng Lin. WC@meso-Pt core–shell nanostructures for fuel cells. Chem. Commun., 2013, 49, 11677--11679] prepares a core-shell structure WC@meso-Pt nano catalyst, which is prepared by mixing a micron-sized ammonium metatungstate hydrate precursor with copper nitrate through spray drying, then self-decomposing the mixture into nano-sized WC@Cu particles in a programmed gas-solid reaction, and then performing a platinum replacement reaction. The mesoporous nanocomposite has higher activity and stability to methanol electrooxidation than commercial Pt/C catalysts. However, the catalytic performance of the core-shell structure WC@meso-Pt nano catalyst in the cooperative hydrogen production of glycerol electrooxidation is not ideal. Aiming at the technical bottleneck, the invention provides a WC@Cu/M composite material suitable for glycerol electrooxidation synergistic hydrogen production and a preparation method thereof. Disclosure of Invention The first technical problem to be solved by the invention is to provide a preparation method of WC@Cu/M composite material, and the composite material prepared by the method has the advantages of stable combination among components, good thermal stability and capability of achieving nano-to-micron level regulation and control of composite material particles so as to adapt to different application environments. The second technical problem to be solved by the invention is to provide a WC@Cu/M composite material. The third technical problem to be solved by the invention is to provide the application of the WC@Cu/M composite material as an electrocatalyst in the cooperative hydrogen production of glycerol electrooxidation. The technical scheme of the invention is specifically described below. In a first aspect, the invention provides a method for preparing a WC@Cu/M composite material, wherein M is noble metal, and the method comprises the following steps: (1) Obtaining nano WC@Cu particles, wherein the weight ratio of Cu to W is 1:3-10, and the particles are of a core-shell structure with WC as a core and Cu as a shell; (2) The nano WC@Cu particles are placed in a muffle furnace and oxidized for 20-40min at 280-300 ℃ in air, so that oxidized WC@Cu particles are obtained; (3)