阅读说明：本技术 一种泡沫镍负载铁镍基复合材料的制备方法及其应用 (Preparation method and application of foam nickel-loaded iron-nickel-based composite material ) 是由 王建芝 喻发全 陈晨 薛亚楠 蔡宁 刘捷 李辉 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种泡沫镍负载铁镍基复合材料的制备方法及其应用,包括如下操作步骤：步骤1：取镍源、铁源、铵源、表面活性剂和泡沫镍超声分散在溶剂A中制备前驱体溶液,将所得的前驱体溶液置于高压釜中在高压环境下反应5-20h,反应完成后冷却至室温,取出后洗涤并干燥即得到氮掺杂的FeNi-LDHs/NF纳米阵列复合材料；步骤2：将步骤1所得FeNi-LDHs/NF纳米阵列复合材料放入MOF的合成溶液中,通过模板定向生长反应在其表面负载MOF粒子,水洗数次后进行干燥即得到FeNi-LDHs/MOF/NF纳米阵列复合材料；步骤3：将步骤2所得FeNi-LDHs/MOF/NF纳米阵列复合材料进行掺磷、掺硫或氧化反应以得到泡沫镍负载铁镍基复合材料。该制备方法操作简单、原料易得,反应条件容易达到。(The invention discloses a preparation method and application of a foam nickel-loaded iron-nickel-based composite material, which comprises the following operation steps: step 1: ultrasonically dispersing a nickel source, an iron source, an ammonium source, a surfactant and foamed nickel in a solvent A to prepare a precursor solution, placing the obtained precursor solution in an autoclave to react for 5-20h under a high-pressure environment, cooling to room temperature after the reaction is finished, taking out, washing and drying to obtain the nitrogen-doped FeNi-LDHs/NF nano-array composite material; step 2: putting the FeNi-LDHs/NF nano-array composite material obtained in the step (1) into a synthesis solution of MOF, carrying MOF particles on the surface of the composite material through template directional growth reaction, washing with water for several times, and drying to obtain the FeNi-LDHs/MOF/NF nano-array composite material; and step 3: and (3) carrying out phosphorus doping, sulfur doping or oxidation reaction on the FeNi-LDHs/MOF/NF nano array composite material obtained in the step (2) to obtain the foam nickel-loaded iron-nickel-based composite material. The preparation method has the advantages of simple operation, easily obtained raw materials and easily achieved reaction conditions.)

1. The preparation method of the foam nickel-loaded iron-nickel-based composite material is characterized by comprising the following operation steps of: step 1: ultrasonically dispersing a nickel source, an iron source, an ammonium source, a surfactant and foamed nickel in a solvent A to prepare a precursor solution, placing the obtained precursor solution in an autoclave to react for 5-20h under a high-pressure environment, cooling to room temperature after the reaction is finished, taking out, washing and drying to obtain the nitrogen-doped carbon-coated FeNi bimetallic compound-loaded FeNi-LDHs/NF nano array composite material;

step 2: putting the FeNi-LDHs/NF nano-array composite material obtained in the step (1) into a synthetic solution of an organic metal framework precursor, carrying MOF particles on the surface of the FeNi-LDHs/NF nano-array composite material through template oriented growth reaction, washing with water for a plurality of times, and drying to obtain the FeNi-LDHs/MOF/NF nano-array composite material coated with the MOF;

and step 3: and (3) carrying out phosphorus doping, sulfur doping or oxidation reaction on the FeNi-LDHs/MOF/NF nano array composite material obtained in the step (2) to obtain the foam nickel-loaded iron-nickel-based composite material.

2. The preparation method of the foam nickel-iron-nickel-supported composite material according to claim 1, wherein the phosphorus doping reaction in the step 3 is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 at 800 ℃ under the protection of inert gas and perform phosphorus doping reaction, and after the reaction is completed, the composite material is allowed to stand and is cooled to room temperature, so that the phosphated three-dimensional foam nickel-iron-nickel-supported composite material is obtained.

3. The method for preparing the foam nickel-supported iron-nickel-based composite material according to claim 2, wherein the raw material for phosphorus doping reaction during calcination in the step 3 is sodium phosphate, sodium phosphite or sodium hypophosphite, wherein the amount of the raw material for phosphorus doping reaction is 1-4 mass ratio to the FeNi-LDHs/MOF/NF nano-array composite material, calculated according to the content of P: 1.

4. the method for preparing the foam nickel-iron-nickel-supported composite material according to claim 1, wherein the sulfurization reaction in the step 3 is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 under the protection of inert gas at the temperature of 300-1000 ℃ for sulfurization reaction, and after the reaction, the composite material is allowed to stand and is cooled to room temperature, so that the sulfurized three-dimensional foam nickel-iron-nickel-supported composite material is obtained.

5. The method for preparing the foam nickel-supported iron-nickel-based composite material according to claim 4, wherein a vulcanizing raw material for the vulcanizing reaction in the step 3 is sodium sulfide or sulfur powder, wherein the mass ratio of the vulcanizing raw material to the FeNi-LDHs/MOF/NF nano-array composite material is 1-10: 1.

6. the method for preparing the foam nickel-iron-nickel-supported composite material according to claim 1, wherein the oxidation reaction in the step 3 is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 in air at 800 ℃ and perform oxidation reaction, and after the reaction, the composite material is stood and cooled to room temperature to obtain the oxidized three-dimensional foam nickel-iron-nickel-supported composite material.

7. The method for preparing the foam nickel-loaded iron-nickel-based composite material according to any one of claims 2 to 6, wherein the calcination in the step 3 is performed by using a tube furnace, the temperature rising speed of the tube furnace is 3-8 ℃/min, the temperature reduction speed of the tube furnace is 3-8 ℃/min, and the heat preservation time is 40-200 min.

8. The method for preparing the foam nickel-supported iron-nickel-based composite material according to any one of claims 1 to 6, wherein the nickel source in the step 1 is nickel nitrate or nickel chloride; the iron source is ferric nitrate or ferric chloride; the ammonium source is one or two of ammonium acetate, ammonium fluoride, ammonium chloride and urea; the surfactant is sodium citrate, cetyl trimethyl ammonium bromide or polyvinylpyrrolidone; the solvent A is water or ethanol.

9. The method for preparing the foam nickel-supported iron-nickel-based composite material according to claim 8, wherein the molar ratio of the nickel source, the iron source, the ammonium source and the solvent A in the precursor solution in the step 1 is 1: 1-2: 8-16: 10-80, the ratio of the mass of the surfactant to the mass of the nickel source is 0-1: 4 g/mmol; the ratio of the surface area of the foamed nickel to the amount of the nickel source is 2.5-8:1cm²/mmol。

10. The method as claimed in claim 8, wherein the autoclave has a reaction temperature of 100-200 ℃ and a reaction time of 5-20 h.

11. The method for preparing the foam nickel-supported iron-nickel-based composite material according to claim 8, wherein the metal source in the synthesis solution in the step 2 is one or two of nitrate, acetate or chloride of cobalt, iron or nickel; the ligand in the synthetic solution is 2-methylimidazole, 1,3,5 tribenzoic acid or p-dibenzoic acid; the solvent B in the synthetic solution is water, ethanol or methanol; the molar ratio of the nickel source to the metal source in the synthesis solution is 1: 1-4; the molar ratio of the metal source, the ligand and the solvent B in the synthesis solution is 1: 1-10: 125-500; the reaction temperature of the template directional growth reaction is 25-150 ℃, and the reaction time is 0.5-24 h.

12. Use of a product of a process for the preparation of a nickel-iron-on-foam composite material according to any one of claims 1 to 11 for the preparation of an electrode.

Technical Field

The invention belongs to the technical field of nano composite materials, and particularly relates to a preparation method of a foam nickel-loaded iron-nickel-based composite material.

Background

With the increasing environmental pollution and energy crisis, the demand of human beings for environment-friendly adsorption materials and efficient energy storage materials is increasing. However, a new material which can simultaneously satisfy two problems of environmental management and new energy development is urgently needed in the world at present. Layered Double Hydroxides (LDHs) are clay materials which are composed of different Double Hydroxides and have Layered microstructures, and due to the unique Layered structures and the interchangeability of metal ions and interlayer anions on laminates, the Layered Double Hydroxides become hot research spots in the fields of water environment treatment, electrochemical energy storage and the like in recent years.

The FeNi-LDHs is a typical layered double hydroxide, not only has the characteristics of large specific surface area, porous structure and the like of the LDHs material, but also has the advantages of low price of raw materials and environmental friendliness, but the electrocatalytic process of the FeNi-LDHs is mainly controlled by a chemical process, and after multiple charge-discharge cycles, part of Ni is subjected to charge-discharge cycles^M+Irreversible transformation occurs, and meanwhile, the top ends of partial nano sheets are bent and deformed, so that effective active sites are reduced, and the circulation stability of the nano sheets is reduced.

The Metal Organic Framework (MOF) is a porous material formed by self-assembling organic ligands containing oxygen or nitrogen elements and transition metal ions through metal-ligand complexation, and has the advantages of great specific surface area, pore volume, ultrahigh porosity, adjustable structure and function and the like. However, the poor thermal, aqueous and chemical stability of MOF materials limits their use in many fields; in addition, the particle size of the MOF material is small, the operation is difficult in the process of repairing water, and the recovery and post-treatment are not easy to occur, so that the use effect is influenced.

Disclosure of Invention

In order to solve the above technical problems, the present invention aims to provide a foamed nickel-supported carbon-rich FeNi-based layered double hydroxide/metal organic framework material derivative

In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a foam nickel-loaded iron-nickel-based composite material comprises the following operation steps: step 1: ultrasonically dispersing a nickel source, an iron source, an ammonium source, a surfactant and foamed nickel in a solvent A to prepare a precursor solution, placing the obtained precursor solution in an autoclave to react for 5-20h under a high-pressure environment, cooling to room temperature after the reaction is finished, taking out, washing and drying to obtain the carbon-coated FeNi-LDHs/NF nano-array composite material;

step 2: putting the FeNi-LDHs/NF nano-array composite material obtained in the step (1) into a synthesis solution of an MOF precursor, carrying MOF particles on the surface of the composite material through template directional growth reaction, washing with water for several times, and drying to obtain the FeNi-LDHs/MOF/NF nano-array composite material;

and step 3: and (3) carrying out phosphorus doping, sulfur doping or oxidation reaction on the FeNi-LDHs/MOF/NF nano array composite material obtained in the step (2) to obtain the foam nickel-loaded iron-nickel-based composite material.

In the technical scheme, the phosphorus doping reaction in the step 3 is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 at 800 ℃ under the protection of inert gas and perform phosphorus doping reaction, and after the reaction is finished, standing and cooling to room temperature, the phosphated three-dimensional foam nickel-loaded iron-nickel-based composite material is obtained. And 3, during calcination in the step 3, the phosphorization raw material for phosphorus doping reaction is sodium phosphate, sodium phosphite or sodium hypophosphite, wherein the dosage of the phosphorization raw material is calculated according to the content of P, and the mass ratio of the phosphorization raw material to the FeNi-LDHs/MOF/NF nano array composite material is 1-4: 1.

in the technical scheme, the step 3 of the sulfur doping reaction is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 under the protection of inert gas at the temperature of 300-1000 ℃ for a vulcanization reaction, and after the reaction, standing and cooling to room temperature, the vulcanized three-dimensional foam nickel-supported iron-nickel-based composite material is obtained. And 3, the vulcanizing raw material for the sulfur doping reaction in the step 3 is sodium sulfide or sulfur powder, wherein the using amount of the vulcanizing raw material is calculated according to the content of S, and the mass ratio of the vulcanizing raw material to the FeNi-LDHs/MOF/NF nano array composite material is 1-10: 1.

in the technical scheme, the oxidation reaction in the step 3 is to calcine the FeNi-LDHs/MOF/NF nano array composite material obtained in the step 2 in the air at the temperature of 300-800 ℃ and perform oxidation reaction, and after the reaction, standing and cooling to the room temperature, the oxidized foam nickel-supported iron-nickel-based composite material is obtained.

And 3, calcining in the step 3 by adopting a tube furnace, wherein the temperature rise speed of the tube furnace is 3-8 ℃/min, the temperature reduction speed is 3-8 ℃/min, and the heat preservation time is 40-200 min.

In the technical scheme, the nickel source in the step 1 is nickel nitrate or nickel chloride; the iron source is ferric nitrate or ferric chloride; the ammonium source is one or two of ammonium acetate, ammonium fluoride, ammonium chloride and urea; the surfactant is cetyl trimethyl ammonium bromide, sodium citrate or polyvinylpyrrolidone; the solvent A is water or ethanol. Wherein the molar ratio of the nickel source, the iron source, the ammonium source and the solvent A in the precursor solution in the step 1 is 1: 1-2: 8-16: 10-80, the ratio of the mass of the surfactant to the mass of the nickel source is 0-1: 4 g/mmol; the ratio of the surface area of the foamed nickel to the amount of the nickel source is 2.5-8:1cm²/mmol。

The reaction temperature of the high-pressure autoclave in the technical scheme is 100-200 ℃, and the reaction time is 5-20 h.

In the technical scheme, the metal source in the synthetic solution in the step 2 is one or two of nitrate, acetate or chloride of cobalt, iron or nickel; the ligand in the synthetic solution is 2-methylimidazole, 1,3,5 tribenzoic acid or p-dibenzoic acid; the solvent B in the synthetic solution is water, ethanol or methanol; the molar ratio of the nickel source to the metal source in the synthesis solution is 1: 1-4; the molar ratio of the metal source, the ligand and the solvent B in the synthesis solution is 1: 1-10: 125-500; the reaction temperature of the template directional growth reaction is 25-150 ℃, and the reaction time is 0.5-24 h.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

(1) the prepared composite catalytic material grows on the surface of a foam nickel skeleton structure, and can be directly used as an electrode when being used as a self-supported catalyst;

(2) in the preparation process of the FeNi-LDHs/NF nano array composite material, the added surfactant can adjust the lamella of the LDHs to form a three-dimensional flower type structure, and carbon is wrapped on the outer layer of the FeNi-LDHs after reaction to prevent the loss of metal ions;

(3) the FeNi-LDHs/NF nano array composite material is used as a template, heterogeneous nucleation growth of MOFs on the corresponding template can be realized, high-quality and orderly-arranged arrays can be obtained, the conductive substrate, MOFs types, the array morphology and the like of the array structure can be changed rationally, and the formed three-dimensional structure improves the electron transmission and proton transmission of the material.

(4) Through calcination and phosphorus doping, sulfur doping or oxidation treatment under different conditions, the FeNi-LDHs/MOF/NF nano array composite material can be derived to obtain a porous carbon-based composite array material, inherits an array structure with orderly arranged matrix materials and a self-supporting multi-level pore structure, can be doped with heteroatoms, breaks up the original arrangement of the composite catalytic material, exposes more active sites, is beneficial to the improvement of the performance of the catalyst, and realizes high-efficiency catalytic efficiency.

(5) The preparation method is simple to operate, raw materials are easy to obtain, reaction conditions are easy to achieve, and the obtained product has a great industrial application prospect.

Drawings

FIG. 1 is a scanning electron microscope image of FeNi-LDHs/NF prepared in example 1 of the present invention;

FIG. 2 is a scanning electron micrograph of FeNi-LDHs/ZIF-67/NF prepared in example 1 of the present invention;

FIG. 3 is a scanning electron micrograph of FeNiP/CoP/NF prepared in example 1 of the present invention;

FIG. 4 is a scanning electron micrograph of FeNiS/FeS/NF prepared in example 2 of the present invention;

FIG. 5 shows FeNiO prepared in example 3 of the present invention_X/CoNiO_XThe chronoamperometric curve of NF under alkaline conditions;

FIG. 6 is a scanning electron microscope image of FeNi-LDHs/NF coated MOF without surfactant prepared in example 4 of the present invention;

FIG. 7 is a scanning electron micrograph of FeNiP/NF prepared in example 4 of the present invention;

FIG. 8 is the electrochemical oxygen evolution performance of examples 1 and 4 of the present invention;

FIG. 9 is a scanning electron micrograph of FeNi-LDHs/NF prepared in example 5 of the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.