阅读说明：本技术 一种热分解法制备含Ni2W3N双金属氮化物复合材料的方法 (Preparation of Ni-containing material by thermal decomposition2W3Method for preparing N bimetal nitride composite material ) 是由 高静 杨佳兴 金秋阳 刘书杰 佟明兴 李国华 于 2019-08-26 设计创作，主要内容包括：本发明涉及热分解法制备含Ni_2W_3N双金属氮化物复合材料的方法：以杂钨酸和有机胺反应生成的杂化物作为前驱体,在氮气和氢气混合气体中煅烧后,制得了含Ni_2W_3N的复合材料Ni_2W_3N/WN。本发明的有益效果主要体现在：(1)本发明提供了一种制备高效电解水析氢的双金属氮化物的方法,制备的双金属氮化物在酸性和碱性体系下同样具有高效的电催化活性；(2)本发明制备工艺简单、操作简便、反应温度要求较低、效率高,在工业化应用方面具有广阔的应用前景。(The invention relates to a thermal decomposition method for preparing Ni-containing 2 W 3 The method of the N bimetal nitride composite material comprises the following steps: the hybrid generated by the reaction of the hetero-tungstic acid and the organic amine is used as a precursor, and is calcined in a mixed gas of nitrogen and hydrogen to prepare the Ni-containing material 2 W 3 Composite material Ni of N 2 W 3 N/WN. The invention has the following beneficial effects: (1) the invention provides a method for preparing a bimetal nitride for efficiently electrolyzing water to generate hydrogen, wherein the prepared bimetal nitride has efficient electrocatalytic activity under acidic and alkaline systems; (2) the preparation method has the advantages of simple preparation process, simple and convenient operation, lower requirement on reaction temperature, high efficiency and wide application prospect in the aspect of industrial application.)

1. Preparation of Ni-containing material by thermal decomposition₂W₃A method of N-bimetal nitride composite, the method comprising:

(1) adding heteropoly acid crystal Na₆K₄[Ni₄(H₂O)₂(PW₉O₃₄)₂]·32H₂Dissolving O in deionized water to obtain a heteropoly acid crystal solution, dissolving dicyandiamide solution in a proper amount of deionized water to obtain a DCA solution, adding the DCA solution into the heteropoly acid crystal solution to obtain a light green solution, stirring for 1-2 h, placing the solution in an oven at 50-60 ℃ for drying to obtain light green precursor powder, grinding the light green precursor powder, and storing the powder in a dryer for later use;

(2) spreading the precursor powder in a porcelain boat, placing the porcelain boat in a quartz boat, and placing the quartz boat in a tubular shapeCarrying out temperature programming calcination in a furnace; the calcination procedure was: firstly, heating at a rate of 2-3 ℃/min under N₂Heating the mixture from room temperature to 500 ℃ in the atmosphere, keeping the temperature for 30-40 min, and heating the mixture at a certain temperature N at a rate of 3-5 ℃/min₂:H₂Heating to 750 ℃ in the atmosphere and preserving heat for 2-3 h; finally in N₂Cooling to room temperature in the atmosphere, taking out the porcelain boat and collecting black powder therein, namely the Ni-containing porcelain boat₂W₃An N bimetal nitride composite material.

2. The process according to claim 1, wherein the mass ratio of the heteropoly acid crystals to dicyandiamide in the step (1) is 1: 1 to 5.

3. The process according to claim 2, wherein the mass ratio of the heteropoly acid crystals to dicyandiamide in the step (1) is 1: 2.

4. the method of claim 1, wherein N is present in step (2)₂:H₂Under atmosphere N₂:H₂The volume ratio is 4 to 19: 1.

5. The method of claim 1, wherein the calcination procedure in step (2) is: first, the temperature is raised at a rate of 2 ℃/min under N₂Heating from room temperature to 500 deg.C under atmosphere, maintaining the temperature for 30min, and heating at a rate of 5 deg.C/min under N₂:H₂Heating to 750 deg.C under atmosphere, maintaining for 3 hr, and adding N₂Cooling to room temperature under the atmosphere.

(I) technical field

The invention relates to a thermal decomposition method for preparing Ni-containing₂W₃Method for preparing N bimetal nitride composite materialThe method is carried out.

(II) background of the invention

Among all the current artificial energy sources, the hydrogen energy source has no pollution to the environment because the reaction product is water, and is clean energy with great development potential. Most of hydrogen energy is still prepared from traditional fossil fuels, so how to prepare hydrogen efficiently and continuously has become a key object of research of researchers. The research of efficient and stable catalysts to reduce hydrogen evolution overpotential has important guiding significance for solving the energy crisis mentioned above.

The thermal decomposition method is a method for decomposing a metal compound at high temperature to generate a metal simple substance and other compounds, compounds with different structures and appearances can be obtained by controlling the temperature, the time and the gas atmosphere in the reaction, the hydrogen evolution performance of the catalyst can be regulated and controlled by regulating and controlling the factors, and the method is very practical particularly when carbide and nitride are prepared at high temperature.

The transition metal nitride has unique physicochemical properties, on one hand, the introduction of N atoms can modify the d orbitals of the parent metal and make them shrink, which will make the electronic structure of the transition metal nitride more similar to that of noble metals such as platinum; on the other hand, since the atomic radius of N atoms is small, it can be inserted into the interstitial space of the lattice to tightly pack metal atoms, thereby improving the electron conductivity thereof. Due to these modified properties of N atoms, transition metal nitrides have been extensively studied and used in applications for hydrogen production from electrolysis of water. Such as bimetallic nitrides, transition metal nitrides with extremely small nanometer dimensions, transition metal nitrides composited with carbon materials into three-dimensional structures. At present, the research on metal nitrides at home and abroad mainly focuses on doping single metal into various carbides, but the composite material containing the atom-level premixed bimetal nitride can be prepared by mixing heteropoly acid and organic amine and then further calcining, and the composite material has high-efficiency catalytic hydrogen evolution capability.

Disclosure of the invention

The invention aims to provide Ni-containing alloy with simple process and low cost₂W₃A preparation method of an N bimetal nitride composite material.

The technical scheme adopted by the invention is as follows:

preparation of Ni-containing material by thermal decomposition₂W₃A method of N-bimetal nitride composite, the method comprising:

(1) adding heteropoly acid crystal Na₆K₄[Ni₄(H₂O)₂(PW₉O₃₄)₂]·32H₂Dissolving O in deionized water to obtain a heteropoly acid crystal solution, dissolving dicyandiamide solution in a proper amount of deionized water to obtain a DCA solution, adding the DCA solution into the heteropoly acid crystal solution to obtain a light green solution, stirring for 1-2 h, placing the solution in an oven at 50-60 ℃ for drying to obtain light green precursor powder, grinding the light green precursor powder, and storing the powder in a dryer for later use;

(2) the precursor powder is flatly paved in a porcelain boat, the porcelain boat is placed in a quartz boat, and the quartz boat is placed in a tube furnace for temperature programmed calcination; the calcination procedure was: firstly, heating at a rate of 2-3 ℃/min under N₂Heating the mixture from room temperature to 500 ℃ in the atmosphere, keeping the temperature for 30-40 min, and heating the mixture at a certain temperature N at a rate of 3-5 ℃/min₂:H₂Heating to 750 ℃ in the atmosphere and preserving heat for 2-3 h; finally in N₂Cooling to room temperature in the atmosphere, taking out the porcelain boat and collecting black powder therein, namely the Ni-containing porcelain boat₂W₃An N bimetal nitride composite material.

In the step (1), the mass ratio of the heteropoly acid crystal to the dicyandiamide is 1: 1-5, preferably 1: 2.

n in step (2)₂:H₂Under atmosphere N₂:H₂The volume ratio is 4 to 19: 1.

The calcination procedure in step (2) is preferably: first, the temperature is raised at a rate of 2 ℃/min under N₂Heating from room temperature to 500 deg.C under atmosphere, maintaining the temperature for 30min, and heating at a rate of 5 deg.C/min under N₂:H₂Heating to 750 deg.C under atmosphere, maintaining for 3 hr, and adding N₂Cooling to room temperature under the atmosphere.

The invention has the following beneficial effects:

(1) the invention provides a method for preparing a bimetal nitride for efficiently electrolyzing water to generate hydrogen, wherein the prepared bimetal nitride has efficient electrocatalytic activity under acidic and alkaline systems;

(2) the preparation method has the advantages of simple preparation process, simple and convenient operation, lower requirement on reaction temperature, high efficiency and wide application prospect in the aspect of industrial application.

(IV) description of the drawings

Fig. 1 is an XRD pattern of a sample of the bimetal nitride composite prepared in example 1.

Fig. 2 is an XRD pattern of a sample of the bimetal nitride composite prepared in example 2.

Fig. 3 is an XRD pattern of a sample of the bimetal nitride composite prepared in example 3.

Fig. 4 is an XRD pattern of a sample of the bimetal nitride composite prepared in example 4.

Fig. 5 is an XRD pattern of a sample of the bimetal nitride composite prepared in example 5.

FIG. 6 shows that the respective values of the bimetal nitride composite material samples prepared in example 1 are 0.5M H₂SO₄And electrocatalytic hydrogen evolution diagram under a 1M KOH system.

FIG. 7 shows that the respective values of the bimetal nitride composite material samples prepared in example 3 are 0.5M H₂SO₄And electrocatalytic hydrogen evolution diagram under a 1M KOH system.

(V) detailed description of the preferred embodiments

The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto: