阅读说明：本技术 一种高活性电解水用四元高熵泡沫及其制备方法 (Quaternary high-entropy foam for high-activity electrolyzed water and preparation method thereof ) 是由 张旭海 吕宙 崔鹏 曾宇乔 郑新健 蒋建清 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种高活性电解水用四元高熵泡沫,属于微纳材料制备技术领域,其成分由Cu、Ni、Co和Fe组成,其中Cu含量为23～27at％,Ni含量为23～27at％,Co含量为23～27at％,Fe含量为23～27at％。本发明还公开了其制备方法。本发明的一种高活性电解水用四元高熵泡沫,具有良好的催化活性,可用于高效的电解水技术,作为水制氢催化剂使用时,该方法制备出的NiCuCoFe高熵合金泡沫表面析氧过电位可低至250mV,远小于普通高熵合金条带、薄膜及表面的水平,也低于市售Ru和In氧化物催化剂水平；本发明的制备方法制备过程无需采用高温、真空等苛刻环境,在5分钟内即可制备出成品,方法简单可靠,原材料价格低廉。(The invention discloses a quaternary high-entropy foam for high-activity electrolyzed water, which belongs to the technical field of micro-nano material preparation and comprises the components of Cu, Ni, Co and Fe, wherein the content of Cu is 23-27 at%, the content of Ni is 23-27 at%, the content of Co is 23-27 at%, and the content of Fe is 23-27 at%. The invention also discloses a preparation method of the composition. The quaternary high-entropy foam for high-activity electrolyzed water has good catalytic activity, can be used In a high-efficiency electrolyzed water technology, and when being used as a catalyst for hydrogen production from water, the surface oxygen evolution overpotential of the NiCuCoFe high-entropy alloy foam prepared by the method can be as low as 250mV, which is far lower than the level of a common high-entropy alloy strip, a film and the surface and is also lower than the level of a commercially available Ru and In oxide catalyst; the preparation method of the invention does not need harsh environments such as high temperature, vacuum and the like in the preparation process, can prepare the finished product within 5 minutes, and has simple and reliable method and low price of raw materials.)

1. A quaternary high-entropy foam for high-activity electrolyzed water is characterized by comprising Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.

2. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 1, wherein: the quaternary high-entropy foam for the high-activity electrolyzed water has three-dimensionally communicated micropores, and the pore diameter of the micropores is within the range of 10-50 um.

3. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 2, wherein: the pore wall of the micron pore is composed of CuNiCoFe dendrites.

4. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 3, wherein: CuNiCoFe dendrite primary dendrite length be 2 ~ 3um, higher dendrite length be 5 ~ 10 nm.

5. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as defined in any one of claims 1 to 4, which is characterized by comprising the following steps:

1) placing the working electrode in CuSO₄、NiSO₄、CoSO₄、Fe₂(SO₄)₃、(NH₄)₂SO₄、Na₃C₆H₅O₇And H₃BO₃Mixing the solution;

2) and carrying out constant-current electrochemical deposition.

6. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as claimed in claim 5, wherein in the step 1), the CuSO is added₄The concentration is 0.003-0.070M, the NiSO₄The concentration of (a) is 0.008-0.210M, and the CoSO₄The concentration is 0.005-0.15M, and the Fe₂(SO₄)₃The concentration of (A) is 0.008 to 0.12M, the (NH)₄)₂SO₄The concentration is 0.4-0.6M, the Na₃C₆H₅O₇The concentration is 0.2-0.4M, the concentration of H₃BO₃The concentration is 0.3-0.5M.

7. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as claimed in claim 5, wherein in the step 2), the quaternary high-entropy foam is preparedThe current density of the constant-current deposition is 0.7-1.2A/cm²The deposition time is 30-3000 s.

Technical Field

The invention belongs to the technical field of micro-nano material preparation, and particularly relates to quaternary high-entropy foam for high-activity electrolyzed water and a preparation method thereof.

Background

The electrolyzed water can simultaneously provide hydrogen and oxygen, and the combination of the hydrogen and the oxygen can generate clean water and simultaneously provide high-density energy, thereby providing a good way for sustainable development and utilization of clean and efficient energy.

However, when the electrolyzed water is used for hydrogen/oxygen evolution, the equilibrium potential is very negative/positive, and the overpotential is very large, especially at the oxygen evolution end, the overpotential is often more than 300 mV. This makes it urgently necessary to use a highly efficient catalyst for water decomposition on the electrode material.

Among the materials developed at present, the most effective hydrogen evolution end is the Pt-based catalyst, and the oxygen evolution end is the oxide of Ru or In. However, such materials are very expensive due to the use of rare metals.

In recent years, non-noble metals and novel carbon-based nano-catalysts are continuously developed to reduce the cost of electrolyzed water. However, most of the materials have the problems of complex preparation process, difficult multi-element doping, large over potential of an oxygen evolution end and the like.

Disclosure of Invention

The purpose of the invention is as follows: the invention provides a quaternary high-entropy foam for high-activity electrolyzed water, which has good catalytic activity and can be used for a high-efficiency water electrolysis technology; the invention also aims to provide a preparation method of the quaternary high-entropy foam for high-activity electrolyzed water, which can prepare the quaternary high-entropy foam for high-catalytic-activity electrolyzed water within 5 minutes without harsh conditions such as high temperature, vacuum and the like; the preparation method is simple, and the CuNiCoFe high-entropy alloy prepared by the method has both nano dendrites and a hierarchical porous structure.

The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:

a quaternary high-entropy foam for high-activity electrolyzed water comprises Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.

Furthermore, the quaternary high-entropy foam for the high-activity electrolyzed water has three-dimensionally communicated micropores, and the pore diameter of the micropores is within the range of 10-50 um.

Furthermore, the pore wall of the micron pore is composed of CuNiCoFe dendrites.

Further, the length of the primary dendrite of the CuNiCoFe dendrite is 2-3 um, and the length of the higher dendrite is 5-10 nm.

Further, the preparation method of the quaternary high-entropy foam for high-activity electrolyzed water comprises the following steps:

1) placing the working electrode in CuSO₄、NiSO₄、CoSO₄、Fe₂(SO₄)₃、(NH4)₂SO₄、Na₃C₆H₅O₇And H₃BO₃Mixing the solution;

2) and carrying out constant-current electrochemical deposition.

Further, in step 1), the CuSO₄The concentration is 0.003-0.070M, the NiSO₄The concentration of (a) is 0.008-0.210M, and the CoSO₄The concentration is 0.005-0.15M, and the Fe₂(SO₄)₃The concentration of (A) is 0.008 to 0.12M, the (NH)₄)₂SO₄The concentration is 0.4-0.6M, the Na₃C₆H₅O₇The concentration is 0.2-0.4M, the concentration of H₃BO₃The concentration is 0.3-0.5M.

Further, in step 2), the constant current deposition is carried outThe flow density is 0.7 to 1.2A/cm²The deposition time is 30-3000 s.

Has the advantages that: compared with the prior art, the quaternary high-entropy foam for high-activity water electrolysis has good catalytic activity, can be used for high-efficiency water electrolysis technology, and when the quaternary high-entropy foam is used as a water hydrogen production catalyst, the surface oxygen evolution overpotential of the NiCuCoFe high-entropy alloy foam prepared by the method can be as low as 250mV, which is far lower than the level of a common high-entropy alloy strip, a film and the surface and is also lower than the level of a commercially available Ru and In oxide catalyst; the preparation method of the invention does not need harsh environments such as high temperature, vacuum and the like in the preparation process, can prepare the finished product within 5 minutes, and has simple and reliable method and low price of raw materials.

Drawings

FIG. 1 is a low-power (inset) and high-power topography (scanning electron microscope) of CuNiCoFe high-entropy alloy foam;

FIG. 2 is a CuNiCoFe high-entropy alloy foam energy spectrum;

FIG. 3 is a linear scanning diagram of oxygen evolution reaction on the surface of CuNiCoFe high-entropy alloy foam.

Detailed Description

The invention is further described with reference to the following figures and specific examples.

A quaternary high-entropy foam for high-activity electrolyzed water comprises Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.

The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 10-50 um.

The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 2-3 um, and the length of the higher dendrite is 5-10 nm.

A preparation method of quaternary high-entropy foam for high-activity electrolyzed water comprises the following steps:

1) placing the working electrode in CuSO₄、NiSO₄、CoSO₄、Fe₂(SO₄)₃、(NH4)₂SO₄、Na₃C₆H₅O₇And H₃BO₃Mixing the solution;

2) and carrying out constant-current electrochemical deposition.

In step 1), CuSO₄The concentration is 0.003-0.070M, NiSO₄The concentration of (A) is 0.008-0.210M, CoSO₄The concentration of Fe is 0.005-0.15M₂(SO₄)₃The concentration of (A) is 0.008-0.12M, (NH)₄)₂The concentration of SO4 is 0.4-0.6M, Na₃C₆H₅O₇The concentration is 0.2-0.4M, H₃BO₃The concentration is 0.3-0.5M.

In the step 2), the current density of the constant-current deposition is 0.7-1.2A/cm²The deposition time is 30-3000 s.