CN-119710786-B - Co-lattice heterostructure catalyst material based on tungsten carbonitride substrate and preparation method thereof

CN119710786BCN 119710786 BCN119710786 BCN 119710786BCN-119710786-B

Abstract

A coherent heterostructure catalyst material based on a tungsten carbonitride substrate and a preparation method thereof belong to the field of catalysts. Preparing solution A containing platinum and doped metal salt, and preparing solution B containing surfactant. The preparation method comprises the steps of placing a WCN substrate sheet in a B solution, heating the B solution to 220-250 ℃, then gradually dropwise adding the A solution into the B solution, reacting at constant temperature until the dropwise adding is finished, stirring and cooling to room temperature, and in-situ generating Pt-based nano catalyst particles with a coherent heterostructure on the WCN nano structure.

Inventors

LI HONGYI
Ran Guangshun
CHANG YUKUN
SONG HUI
YANG ZICONG
ZHANG YINQUAN
Xiao Yinglan
RAN YUCHANG

Assignees

北京工业大学

Dates

Publication Date: 20260508
Application Date: 20250120

Claims (4)

1. The preparation method of the coherent heterostructure catalyst material based on the tungsten carbonitride substrate is characterized by comprising the following steps of: (1) Placing the platinum-containing salt and the salt corresponding to the doped metal into water, stirring and carrying out ultrasonic treatment, and uniformly dispersing to obtain a solution A; (2) Adding a small amount of surface active protective agent into a container, stirring until the surface active protective agent is completely dissolved and marking the solution as B, taking triethylene glycol as a reducing agent and a solvent to provide a reduction reaction environment for a subsequent metal precursor, adding polyvinylpyrrolidone (PVP) as the surface active protective agent, and increasing catalyst nucleation sites on a substrate material, so that catalyst crystals are easier to grow in situ on the substrate; (3) Preparing a flaky tungsten carbonitride WCN as a substrate material; (4) Placing a substrate sheet in a solution B, heating the solution B to 220-250 ℃, then gradually dropwise adding the solution A into the solution B, reacting at constant temperature until the solution A is completely dripped, stirring and cooling to room temperature, and thus in-situ generating Pt-based nano catalyst particles with a coherent heterostructure on the WCN nano structure; The doping metal in the step (1) is copper, cobalt, nickel and zinc, wherein the concentration of the copper, cobalt, nickel and zinc is 1-20 times of the concentration of platinum, and the concentration of the platinum is 1-5mM.
2. The method for preparing the tungsten carbonitride substrate-based coherent heterostructure catalyst material, according to claim 1, wherein in the step (4), each cm 2 of tungsten carbonitride WCN substrate corresponds to in-situ growth of 5-20 mug of platinum.
3. A coherent heterostructure catalyst material based on a tungsten carbonitride substrate prepared according to the method of any one of claims 1-2.
4. Use of a tungsten carbonitride substrate based coherent heterostructure catalyst material prepared according to the method of any one of claims 1-2 directly as a Hydrogen Evolution Reaction (HER) electrocatalytic electrode for water electrolysis to produce hydrogen.

Description

Co-lattice heterostructure catalyst material based on tungsten carbonitride substrate and preparation method thereof Technical Field The invention relates to the technical preparation and application field of electrocatalytic materials, in particular to a catalyst composite thin film electrode electrocatalytic hydrogen evolution material with a coherent heterostructure and a synthesis method for in-situ growth of the catalyst composite thin film electrode electrocatalytic hydrogen evolution material. Background Electrocatalytic water splitting is a promising technique for producing clean hydrogen fuels. The development of cost-effective, efficient, durable Hydrogen Evolution Reaction (HER) electrocatalysts plays an important role in the electrolysis of water. Platinum-based electrocatalysts exhibit good electrocatalytic activity in both acidic and basic media, but economic costs limit their further use. Recent studies have shown that heterostructure electrocatalysts also exhibit the potential for highly efficient electrocatalytic hydrogen evolution. The matching degree of the interface of the heterostructure electrocatalyst influences the interface electronic structure of the heterostructure electrocatalyst, and therefore the kinetics and the activity of the hydrogen evolution reaction are determined. Therefore, developing a method for constructing a coherent interface heterostructure electrocatalyst for electrocatalytic hydrogen evolution reaction is of great significance and is also challenging. Disclosure of Invention Aiming at the defects or improvement demands of the prior art, the invention provides a method for in-situ synthesis of a coherent heterostructure nano catalyst composite membrane electrode material, which aims to construct a coherent interface structure of a catalyst and a substrate material, promote interface charge distribution and transfer, and further improve the activity and stability of the nano catalyst, thereby solving the technical problem of performance degradation in an electrocatalytic process. In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing and synthesizing a coherent heterostructure catalyst composite electrode, comprising the steps of: (1) Placing the platinum-containing salt and the salt corresponding to the doped metal into water, stirring and carrying out ultrasonic treatment, and uniformly dispersing to obtain a solution A; (2) Adding a small amount of surface active protective agent into a container, stirring until the surface active protective agent is completely dissolved and marking the solution as B, taking triethylene glycol as a reducing agent and a solvent to provide a reduction reaction environment for a subsequent metal precursor, adding polyvinylpyrrolidone (PVP) as the surface active protective agent, and increasing catalyst nucleation sites on a substrate material, so that catalyst crystals are easier to grow in situ on the substrate; (3) Preparing or purchasing flaky tungsten carbonitride (WCN) as a base material; Patent 202311680121.0 discloses a preparation method of a nanoscale high-conductivity tungsten carbonitride heterojunction film, which is used for preparing tungsten carbonitride (WCN) with high specific surface area as a substrate material for in-situ growth of a subsequent Pt-based catalyst according to the flow; (4) Placing a substrate sheet in a solution B, heating the solution B to 220-250 ℃, then gradually dropwise adding the solution A into the solution B, reacting at constant temperature until the solution A is completely dripped, stirring and cooling to room temperature, and thus in-situ generating Pt-based nano catalyst particles with a coherent heterostructure on the WCN nano structure; The doping metal in the step (1) is one or more of copper, cobalt, nickel and zinc, preferably four, wherein the concentration of the copper, cobalt, nickel and zinc is 1-20 times of the concentration of platinum, and the concentration of the platinum is 1-5mM; in the step (2), 1-1.2 g of PVP is correspondingly added to every 100-300 mL of triethylene glycol solution. In the further step (4), 5-20 mug of platinum is correspondingly grown in situ on each cm 2 area of tungsten carbonitride (WCN) substrate. The platinum loading was low. The tungsten carbonitride substrate-based coherent heterostructure catalyst material obtained by the invention is directly used as a Hydrogen Evolution Reaction (HER) electrocatalytic electrode for hydrogen production by water electrolysis. Compared with the prior art, the invention has the advantages and remarkable effects that: (1) The invention prepares the Pt-based nano catalyst composite thin film electrode material with the coherent heterostructure for the first time (the interface between the prepared Pt-based catalyst and the WCN substrate material has coherent relation). The coherent interface structure can redistribute electrons at the