阅读说明：本技术 水分解催化剂用ab2型金属间化合物、合成方法及其应用 (AB for water-splitting catalyst2Intermetallic compound, synthesis method and application thereof ) 是由 李丹 孙念祖 张鹏 吉沈晶 张冬 于 2020-12-25 设计创作，主要内容包括：本发明提供了一种水分解催化剂用AB-2型金属间化合物、合成方法及其应用,其步骤为：(1)于手套箱中,按比例称量A、B两种金属粉末或块材；(2)如果A、B为粉末,则将粉末混合均匀后倒入磨具内,压片,如果A、B为块材,则将两块块材叠放在一起,如果A、B其中一种为粉末,另一种为块材,则将粉末倒入磨具内,压片,将所得压片与所述块材叠放在一起；(3)采用氩弧焊技术使步骤(2)所得样品完全熔融,待冷却后取出。以该催化剂作为工作电极,在碱性或酸性条件下电催化分解水产氢产氧。该催化剂合成过程简单,具有较多的表面活性位点,并在电催化水分解反应中具有优越的性能,适合应用于电催化水分解领域。(The invention provides an AB for a water decomposition catalyst 2 The intermetallic compound, its synthetic method and application, its step is: (1) a, B two kinds of metal powder or blocks are weighed in a glove box according to the proportion; (2) mixing A, B powder, pouring into a grinding tool, tabletting, if A, B is block, stacking two blocks, if A, B is powder, and if another is block, pouring powder into the grinding tool, tabletting, and stacking the obtained tablet and the block; (3) and (3) completely melting the sample obtained in the step (2) by adopting an argon arc welding technology, and taking out after cooling. The catalyst is used as a working electrode, and the hydrogen is produced by electrocatalytic decomposition of water under alkaline or acidic conditions. The catalyst has simple synthesis process, more surface active sites, excellent performance in electrocatalytic water decomposition reaction, and suitability for electrocatalytic water decompositionThe field of solution.)

1. AB₂A method for synthesizing an intermetallic compound, wherein A = RE, Ti, Zr, Hf, Nb, Ta, and B = Cr, Mn, Fe, Co, Ni, Ru, Re, Os, Ir, comprising the steps of:

(1) a, B two kinds of metal powder or blocks are weighed in a glove box according to the proportion of 1:2 of the materials;

(2) mixing A, B powder, pouring into a grinding tool, tabletting, if A, B is block, stacking two blocks, if A, B is powder, and if another is block, pouring powder into the grinding tool, tabletting, and stacking the obtained tablet and the block;

(3) and (3) completely melting the sample obtained in the step (2) by adopting an argon arc welding technology, and taking out after cooling.

2. The method of claim 1, wherein the argon arc welding current is 30-60A.

3. AB synthesised according to the method of claim 1 or 2₂And an intermetallic compound of type (II).

4. AB synthesised according to the method of claim 1 or 2₂The application of intermetallic compound in electrocatalytic decomposition of water to produce hydrogen and oxygen.

5. The use of claim 4, wherein the AB is used₂The intermetallic compound is used as a working electrode, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode system is adopted, and water is subjected to electrocatalytic decomposition under alkaline or acidic conditions under the assistance of an electric field to produce hydrogen and oxygen.

Technical Field

The invention relates to a high-performance water decomposition catalystAB for preparation₂The formula of the intermetallic compound (A = RE, Ti, Zr, Hf, Nb, Ta, B = Cr, Mn, Fe, Co, Ni, Ru, Re, Os, Ir), the synthesis method and the application belong to the technical field of electrocatalysis.

Background

Since the consumption of fossil fuels brings about serious environmental pollution and human energy shortage, the search for sustainable clean energy and energy conversion technologies has never been stopped. Electrocatalytic water decomposition is receiving wide attention because of its advantages of low cost and zero emission. Through intensive research, the metal has strong catalytic effect on water decomposition reaction. Among them, the noble metal Pt is called a zero potential catalyst, and platinum-based catalysts are put to commercial use in reality, and the noble metal (Ru, Os, Ir) -based catalytic water splitting field also plays a significant role. However, the large-scale industrial application of noble metal materials in electrochemical water splitting is severely limited due to the small reserves and high cost of the noble metal materials.

With the development of research, cheap transition metals (Cr, Mn, Fe, Co and Ni) also become a new favorite in the water decomposition industry, and become good carriers of new catalysts due to low price and abundant reserves. However, the research is still focused on finding a stable and efficient electrochemical water decomposition catalyst with simple synthesis.

Disclosure of Invention

The invention aims to provide a high-efficiency water decomposition catalyst AB₂An intermetallic compound and a method for synthesizing the same.

The above AB₂The hydro-electric catalyst for decomposing intermetallic compound and its synthesis process include the following steps:

(1) precisely weighing A, B two kinds of metal powder or blocks in a glove box according to the proportion of 1:2 of the substances;

(2) mixing A, B powder, pouring into grinding tool, tabletting, if A, B is block, stacking two blocks together, if A, B is powder, pouring powder into grinding tool, tabletting, and stacking the obtained tablet and block together;

(3) and (3) under the argon atmosphere, completely melting the sample obtained in the step (2) by adopting an argon arc welding technology, and taking out the sample after cooling.

Preferably, the argon arc welding current is 30-60A, and the current can be properly increased by metal with too high melting point.

The above AB₂The application of intermetallic compound in electrocatalytic decomposition of water to produce hydrogen and oxygen.

In particular, AB obtained by the preparation₂The intermetallic compound is used as a working electrode, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a three-electrode reaction device is adopted to carry out electrocatalytic decomposition on water under alkaline or acidic conditions under the assistance of an electric field to produce hydrogen and oxygen.

Compared with the prior art, the AB₂The intermetallic compound has simple synthesis process, more surface active sites, excellent performance in the hydrogen and oxygen production process of water by electrocatalytic decomposition, and is very suitable for the field of electrocatalytic decomposition of water.

Drawings

FIG. 1 shows HfRe obtained in examples 1 and 2₂And ZrRe₂XRD spectrum of (1).

FIG. 2 is a linear sweep voltammogram of examples 1 and 2 when hydrogen is evolved under acidic conditions.

FIG. 3 is a linear sweep voltammogram of examples 1 and 2 when hydrogen is evolved under basic conditions.

FIG. 4 shows PrNi obtained in example 3₂XRD spectrum of (1).

FIG. 5 is a linear sweep voltammogram of example 3 during hydrogen evolution under basic conditions.

FIG. 6 shows NbCo obtained in example 4₂XRD spectrum of (1).

FIG. 7 is a linear scanning voltammogram of example 4 during oxygen evolution under acidic conditions.

Detailed Description

The invention is further illustrated by the following figures and examples.

Example 1

Synthesis of HfRe₂

Weighing the mass of the hafnium particles in a glove box by using an analytical balance, then calculating the mass of the required hafnium particles and rhenium powder according to the molar ratio of 1:2, pouring the weighed powder into a die, and pressing the die into a wafer with the diameter of 8 mm by using a tablet press.

Secondly, stacking the pressed sheets and the hafnium particles together, placing the sheets and the hafnium particles on a copper base station, enabling the sample to be melted into a uniform spherical shape after fully reacting through argon arc welding, and taking out the sample after cooling.

The synthesized sample was ground into powder and then measured using an X-ray diffraction apparatus. The scanning speed is 5 DEG/min, and the measuring range is measured in a range of 20-60 DEG in terms of 2 theta. The XRD spectrum measured is shown in fig. 1.

To evaluate HfRe prepared by the above method₂The electrochemical performance of the method is applied to electrocatalytic decomposition of water to produce hydrogen under acidic and alkaline conditions, and the method comprises the following specific steps:

at 0.5M H₂SO₄In the solution, a three-electrode reaction device is adopted to prepare the obtained HfRe₂The powder is ground into powder, the powder is pressed into a thin sheet with the diameter of 8 mm, the thin sheet is clamped on an electrode to be used as a working electrode, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and under the assistance of an electric field, the current changes along with the voltage when the water is subjected to electrocatalytic decomposition to produce hydrogen in a test solution, namely, the linear sweep voltammetry is carried out, and the result is shown in figure 2.

Preparing the obtained HfRe in a 1M KOH solution by adopting a three-electrode reaction device₂The powder is ground into powder and pressed into a thin sheet with the diameter of 8 mm, the thin sheet is clamped on an electrode to be used as a working electrode, a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and under the assistance of an electric field, the current changes along with the voltage when the water is electro-catalytically decomposed in a test solution to produce hydrogen, and the result is shown in figure 3.

Example 2

Synthesis of ZrRe₂

Firstly, accurately weighing zirconium powder and rhenium powder in a glove box by an analytical balance according to a molar ratio of 1:2, uniformly mixing the weighed powders, pouring the mixed powders into a die, and pressing the die into a wafer with the diameter of 8 mm by using a tablet press.

Secondly, the pressed sheet is placed on a copper base station, the sample is melted into a uniform spherical shape after being fully reacted through argon arc welding, and the sample is taken out after cooling.

The synthesized sample was ground into powder and then measured using an X-ray diffraction apparatus. The scanning speed is 5 DEG/min, and the measuring range is measured in a range of 20-60 DEG in terms of 2 theta. The XRD spectrum obtained is shown in figure 1 and HfRe obtained in example 1₂The comparison shows.

ZrRe prepared by the method₂The method is applied to electrocatalytic decomposition of water to produce hydrogen under acidic and alkaline conditions, and comprises the following specific steps:

at 0.5M H₂SO₄In the solution, a three-electrode reaction device is adopted to prepare the obtained ZrRe₂Grinding the materials into powder, pressing the powder into a thin sheet with the diameter of 8 mm, clamping the thin sheet on an electrode to be used as a working electrode, taking a carbon rod as a counter electrode and taking a saturated calomel electrode as a reference electrode, and testing the change of current along with voltage when electrocatalytic decomposition of water into hydrogen is carried out in a solution under the assistance of an electric field. The resulting linear cyclic voltammograms were tested against HfRe as in example 1₂The comparison shows that the results are shown in FIG. 2.

ZrRe prepared by adopting a three-electrode reaction device in 1M KOH solution₂Grinding the powder into powder, pressing the powder into a sheet with the diameter of 8 mm, clamping the sheet on an electrode to be used as a working electrode, taking a carbon rod as a counter electrode and taking a saturated calomel electrode as a reference electrode, and testing the change of current along with voltage when electrocatalytic decomposition of water into hydrogen is carried out in a solution under the assistance of an electric field. The resulting linear cyclic voltammograms were tested against HfRe as in example 1₂The comparison shows that the results are shown in FIG. 3.

Example 3

Synthesis of PrNi₂

Weighing the mass of proper praseodymium metal in a glove box by using an analytical balance, then calculating the mass of the required nickel powder according to the proportion of 1:2, pouring the weighed powder into a die, and pressing the powder into a wafer with the diameter of 8 mm by using a tablet press.

Secondly, stacking the pressed sheet and the praseodymium block together, placing the sheet and the praseodymium block on a copper base station, enabling the sample to be melted into a uniform spherical shape after fully reacting through argon arc welding, and taking out the sample after cooling.

The synthesized sample was ground into powder and then measured using an X-ray diffraction apparatus. The scanning speed is 5 DEG/min, and the measuring range is measured in a range of 25 DEG to 55 DEG in terms of 2 theta. The XRD spectrum measured is shown in fig. 4.

The sample prepared by the method is applied to electrocatalytic decomposition of water to produce hydrogen under alkaline conditions, and the method comprises the following specific steps:

in a 1M KOH solution, a three-electrode reaction device is adopted, a prepared sample is ground into powder and pressed into a thin sheet with the diameter of 8 mm, the thin sheet is clamped on an electrode to serve as a working electrode, a carbon rod serves as a counter electrode, a saturated calomel electrode serves as a reference electrode, and the current changes along with the voltage when water is decomposed into hydrogen through electrocatalysis in the solution to be tested under the assistance of an electric field. The linear cyclic voltammogram obtained from the test is shown in FIG. 5.

Example 4

Synthesis of NbCo₂

Firstly, weighing a proper amount of cobalt tablets in a glove box by using an analytical balance, then calculating the mass of the required niobium powder according to the proportion of 1:2, pouring the weighed powder into a die, and pressing the powder into round tablets with the diameter of 8 mm by using a tablet press.

Secondly, the pressed sheet and the cobalt sheet are stacked together and placed on a copper base station, the sample is melted into a uniform spherical shape after fully reacting through argon arc welding, and the sample is taken out after cooling.

The synthesized sample was ground into powder and then measured using an X-ray diffraction apparatus. The scanning speed is 5 DEG/min, and the measuring range is measured in a range of 30-50 DEG in terms of 2 theta. The XRD spectrum measured is shown in fig. 6.

The sample prepared by the method is applied to electrocatalytic decomposition of water under acidic conditions to produce oxygen, and the method comprises the following specific steps:

at 0.5M H₂SO₄In the solution, a three-electrode reaction device is adopted, a prepared sample is ground into powder and pressed into a sheet with the diameter of 8 mm, the sheet is clamped on an electrode to serve as a working electrode, a carbon rod serves as a counter electrode, a saturated calomel electrode serves as a reference electrode, and the current changes along with the voltage when water is decomposed through electrocatalysis in the solution to produce oxygen under the assistance of an electric field. The linear cyclic voltammogram obtained from the test is shown in FIG. 7.