CN114959787A - Nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material and preparation method and application thereof - Google Patents
Nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material with in-situ growth of foamed nickel, and a preparation method and application thereof, and belongs to the field of inorganic materials. The nickel sulfide and the molybdenum disulfide are compounded to form a hollow sphere structure, active sites are fully exposed, and the nickel sulfide and the molybdenum disulfide are cooperatively catalyzed to jointly enhance the electrocatalytic oxygen evolution performance. In the construction process of the nickel sulfide/molybdenum disulfide hollow sphere in-situ growth of the foamed nickel, the invention adopts a one-step hydrothermal method, has simple process and is beneficial to large-scale production.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material grown in situ by using foamed nickel, and a preparation method and application thereof.
Background
With the increasing consumption of fossil fuels and increasing energy demand, it is increasingly important to develop sustainable energy conversion and storage systems, such as water-splitting devices, metal-air batteries, and the like. Electrocatalytic water decomposition includes two processes of oxidation and reduction of water, however, since a large overpotential is required for the oxygen evolution reaction, the overpotential needs to be reduced by an electrocatalyst in the process, and energy loss is reduced. RuO 2 And IrO 2 Is a good electro-catalytic oxygen evolution catalyst, but is difficult to be applied in large scale in commerce due to the problems of poor stability, overhigh cost, low selectivity and the like. Therefore, it is a critical technology to find a durable, efficient, low-cost and environmentally friendly catalyst. The hydrothermal reaction is a common method for material synthesis due to the characteristic of simple process. Method for stacking three-dimensional porous NiSe on surface of foamed nickel by using one-step hydrothermal method in 2015 by Zhou and collaborators thereof 2 For electrocatalytic materials. However, it is difficult to control the micro-morphology of the material during the hydrothermal reaction, thereby affecting the electrocatalytic performance.
The material with the hollow sphere structure has very important application prospect in the field of catalysis due to the special morphology and the higher specific surface area. The hollow sphere structure is prepared by a template method, including a hard template method and a soft template method. Among them, the hard template method usually uses polymer, metal particles and inorganic nonmetal as hard templates to prepare the hollow sphere structure. However, it is difficult to remove the hard template during the fabrication process, and the commonly used removal methods are chemical etching and thermal sintering, but these methods are complicated in steps and are not environmentally friendly. In contrast, the soft template is easier to remove, but is also easy to deform, thereby causing the problems of poor dispersibility, unstable morphology and the like of the hollow spheres. Therefore, finding a suitable soft template is crucial to the synthesis of the ideal hollow sphere structure. The soft templates for synthesizing the hollow sphere structure are usually provided with surfactants, bubbles, emulsion droplets, polymer vesicles, polymer aggregates and the like. Wherein, the surfactant molecules can easily form micelles, vesicles, droplets and the like in aqueous solution and can be used as a template for synthesizing a hollow sphere structure. The nonionic surfactant is a common surfactant, and is one of the choices of soft templates due to the advantages of high stability, abundant raw material sources, good compatibility, wide applicable pH value range and the like. Although some surfactant-based templates have been studied in recent years to control the morphology, uniformity and size of hollow spheres, control of the structure of hollow spheres remains a significant challenge as the stability and structure of micelles and vesicles are affected by many factors, such as solution ionic strength and solvent polarity.
At present, no relevant report that the nickel sulfide/molybdenum disulfide hollow sphere structure three-dimensional composite material grows in situ on the foamed nickel and is directly applied to the electrocatalytic oxygen evolution reaction is found.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material by foam nickel in-situ growth, which comprises the following steps:
1) cutting the foamed nickel into blocks, washing to remove nickel oxide and grease, and drying to prepare blocky foamed nickel;
2) dissolving thioacetamide, anhydrous sodium molybdate and a nonionic triblock copolymer surfactant in deionized water to obtain a mixed solution, and putting the massive foam nickel prepared in the step 1) into the mixed solution to be fully and uniformly mixed at room temperature;
3) and (3) preserving the heat of the uniformly mixed solution obtained in the step 2) at 200 ℃ for 24 hours, washing and drying to obtain the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere structure three-dimensional composite material.
Preferably, in step 1), the nickel foam is cut into rectangular blocks.
Further preferably, the rectangular nickel foam has a size of 2cm × 4cm, a thickness of 1.0mm, and a pore size of 120 ppi.
Preferably, in step 1), washing is performed by sequentially washing with acetone, hydrochloric acid, deionized water and ethanol.
Preferably, in the step 2), the mass ratio of thioacetamide, anhydrous sodium molybdate and the nonionic surfactant is 4:3: 7.
Further preferably, the nonionic surfactant employs triblock copolymer L31, P123 or F127.
Preferably, in step 3), the uniformly mixed solution is heated to 200 ℃ from room temperature at a rate of 10 ℃/min.
Preferably, in step 2), the integrated foam is washed with deionized water, ethanol.
The invention also discloses a nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material prepared by the preparation method of the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material, wherein the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material is porous/compact, hollow spheres are uniformly distributed, and the diameter of the hollow spheres is 7-30 micrometers; the surface of the hollow sphere is composed of a plurality of rice-shaped particles with the length of about 100 nm; the thickness of the spherical shell of the hollow sphere is 200 nm-1 μm.
The invention also discloses an application of the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material in preparing an electrocatalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material by foam nickel in-situ growth, which is characterized in that based on triblock copolymer surfactant micelles, nickel sulfide/molybdenum disulfide porous hollow spheres which are uniformly distributed are grown in situ on foam nickel by a one-step hydrothermal method. The non-ionic triblock copolymer surfactant with the combination of hydrophilic polyethylene oxide and hydrophobic polypropylene oxide is used as a structure directing agent to obtain a hollow sphere structure with high specific surface area and controllable shape, so that the high specific surface area is obtained. When the concentration of the surfactant reaches a certain value, a large number of ordered molecular aggregates-micelles taking hydrophobic groups as cores and hydrophilic groups as shells are formed, and usually 50-100 molecules form one micelle. And (3) reacting sulfur ions generated by thioacetamide with nickel exposed on the surface of the foam nickel to generate nickel sulfide, further reacting with molybdenum ions decomposed by anhydrous sodium molybdate to generate molybdenum sulfide, forming a hollow spherical structure along the surface of the spherical micelle, and then washing with deionized water and ethanol to remove the micelle template. Through in-situ growth, good connection is formed between the foamed nickel and the nickel sulfide/molybdenum disulfide hollow spheres, so that the stability and the conductivity of the material are improved, and the method is simple in process and beneficial to large-scale production.
The invention discloses an electrocatalyst formed by foamed nickel in-situ growth nickel sulfide/molybdenum disulfide hollow spheres as an integral electrode, a triblock nonionic surfactant as a soft template fully utilizes the special appearance and large specific surface area of the hollow sphere structure to fully expose active sites, and simultaneously, the nickel sulfide and the molybdenum disulfide are compounded and cooperatively catalyzed to jointly enhance the electrocatalytic oxygen evolution performance. Structurally, the nickel sulfide/molybdenum disulfide hollow sphere structure grows on holes of the conductive three-dimensional foam nickel in situ, and the obtained three-dimensional electrode structure has a larger catalyst loading surface area and is beneficial to improving the electrocatalytic oxygen evolution efficiency.
Drawings
FIG. 1 is an SEM image of a foamed nickel in-situ grown nickel sulfide/molybdenum disulfide crushed hollow sphere electrocatalyst prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a nickel foam in-situ grown nickel sulfide/molybdenum disulfide porous hollow sphere electrocatalyst prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a nickel foam in-situ grown nickel sulfide/molybdenum disulfide dense hollow sphere electrocatalyst prepared in example 3 according to the present invention;
FIG. 4 is an X-ray diffraction pattern of a nickel foam in-situ grown nickel sulfide/molybdenum disulfide composite hollow sphere electrocatalyst (corresponding to curves a, b, and c, respectively) prepared in examples 1, 2, and 3 of the present invention;
FIG. 5 is an oxygen evolution polarization curve of the nickel foam in-situ grown nickel sulfide/molybdenum disulfide composite hollow sphere electrocatalyst, pure molybdenum disulfide and nickel foam prepared by the invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
A preparation method of a nickel foam in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere comprises the following steps of dissolving 60mg of Thioacetamide (TAA), 45mg of anhydrous sodium molybdate and 105mg of a nonionic surfactant E2P16E2(L31, HLB is 1-7) in 30mL of deionized water, then placing cleaned rectangular nickel foam into the mixed solution, and magnetically stirring at room temperature for 30 minutes. The prepared solution was transferred to a 50mL teflon lined stainless steel autoclave, heated to 200 ℃ and held for 24 hours, with the nickel sulfide/molybdenum disulfide growing in situ on the nickel foam. The integrated foam was then washed with deionized water, ethanol and then dried in a vacuum oven at 60 ℃ for 12 hours.
A typical three-electrode system is adopted to test the catalytic oxygen evolution performance of the electrocatalyst of the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere, 1cm multiplied by 1cm of foamed nickel/nickel sulfide/molybdenum disulfide hollow sphere composite material is directly used as a working electrode, a graphite rod electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and 1.0M KOH is used as electrolyte. The scanning rate is 5mV s -1 The polarization curve of the electrocatalyst was tested at a current density of 50mA cm -2 The corresponding overpotential and Tafel slopes were 375mV and 73 mV/dec.
Referring to fig. 1, for the electrocatalyst with foamed nickel in-situ grown nickel sulfide/molybdenum disulfide crushed hollow spheres prepared in this example, a small amount of crushed hollow sphere structures with smaller diameters were observed when using the nonionic surfactant L31 as a soft template. The smaller the L31 template molecule, the fewer hydrophilic groups and the smaller the micelle size, the fewer surface cavities for accommodating guest molecules, resulting in fewer nickel sulfide/molybdenum disulfide molecules on the micelle surface. Therefore, it is difficult for the nickel sulfide/molybdenum disulfide to form stable and complete spherical structures along the micelles of the L31 template. The curve a in FIG. 4 is its X-ray diffraction pattern, and analysis shows that the product mainly contains Ni and Ni 3 S 2 ，MoS 2 The content is less.
Referring to fig. 5, the result of the catalytic oxygen evolution performance of the electrocatalyst of the hollow nickel sulfide/molybdenum disulfide composite sphere prepared in this embodiment shows that the catalytic oxygen evolution performance of the catalyst prepared in the present invention is significantly better than that of pure molybdenum disulfide and pure nickel foam, which indicates that the hollow nickel foam/nickel sulfide/molybdenum disulfide composite sphere can significantly improve the electrocatalytic activity.
Example 2
A preparation method of a nickel sulfide/molybdenum disulfide composite hollow sphere with foamed nickel in-situ growth comprises the following steps of dissolving 60mg of thioacetamide, 45mg of anhydrous sodium molybdate and 105mg of a nonionic surfactant E20P70E20(P123, HLB is 7-12) in 30mL of deionized water, then placing prepared rectangular foamed nickel into the mixed solution, and magnetically stirring at room temperature for 30 minutes. The prepared solution was transferred to a 50mL teflon lined stainless steel autoclave, heated to 200 ℃ and held for 24 hours, with the nickel sulfide/molybdenum disulfide growing in situ on the nickel foam. The integrated foam was then washed with deionized water, ethanol and then dried in a vacuum oven at 60 ℃ for 12 hours.
Referring to fig. 2, for the electrocatalyst of the nickel foam in-situ growth nickel sulfide/molybdenum disulfide porous hollow sphere prepared in this example, when the non-ionic surfactant P123 was used as a soft template, more and larger hollow sphere structure was observed to grow in-situ on the nickel foam, wherein the hollow sphere is porous. The porous hollow spheres are uniformly distributed, the diameters of the porous hollow spheres are 7-9 mu m, and the surfaces of the porous hollow spheres consist of a plurality of rice-shaped particles with the lengths of about 100nm, so that more active sites are provided. The P123 template has larger molecules and a proper amount of surface cavities, so that a proper spherical micelle is formed, and the nickel sulfide/molybdenum disulfide nanoparticles are gathered along the surface of the spherical micelle and developed into the porous hollow sphere. The curve b in FIG. 4 is the X-ray diffraction pattern, and the analysis shows that the product mainly contains Ni and Ni 3 S 2 、MoS 2 。
A typical three-electrode system is adopted to test the catalytic oxygen evolution performance of the electrocatalyst of the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere, 1cm multiplied by 1cm of foamed nickel/nickel sulfide/molybdenum disulfide hollow sphere composite material is directly used as a working electrode, a graphite rod electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and 1.0M KOH is used as electrolyte. The scanning rate is 5mV s -1 The polarization curve of the electrocatalyst was tested at a current density of 50mA cm -2 The corresponding overpotential and Tafel slopes were 314mV and 57 mV/dec.
Example 3
A preparation method of a nickel foam in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere comprises the following steps of dissolving 60mg of Thioacetamide (TAA), 45mg of anhydrous sodium molybdate and 110mg of a nonionic surfactant E91P69E91(F127, HLB is 13-18) in 30mL of deionized water, then placing the prepared rectangular nickel foam into the mixed solution, and magnetically stirring at room temperature for 30 minutes. The prepared solution was transferred to a 50mL teflon lined stainless steel autoclave, heated to 200 ℃ and held for 24 hours, with the nickel sulfide/molybdenum disulfide growing in situ on the nickel foam. The integrated foam was then washed with deionized water, ethanol and then dried in a vacuum oven at 60 ℃ for 12 hours.
Referring to fig. 3, for the electrocatalyst made in this example, in which nickel sulfide/molybdenum disulfide dense hollow spheres are grown in situ, when F127 nonionic surfactant is used as a soft template, large and intact hollow spheres are observed, wherein the nickel sulfide/molybdenum disulfide hollow spheres are not uniform in size. Because the F127 molecules are large, the micelle surface consists of a large number of hydrophilic groups, and the micelle has a large surface cavity, so that the growth of nickel sulfide/molybdenum disulfide nanoparticles is facilitated. Therefore, a large number of complete hollow sphere structures with large size and high hardness are prepared. The diameter of part of the hollow spheres is larger than 30 μm, the thickness of the hollow sphere shell is about 1 μm, and is far larger than that (200nm) of the P123 template, and the specific surface area is lower in comparison. Many lumps of about 200nm in size were observed on the surface of the hollow sphere. The curve c in FIG. 4 is the X-ray diffraction pattern, and the analysis shows that the product mainly contains Ni and Ni 3 S 2 、MoS 2 。
A typical three-electrode system is adopted to test the catalytic oxygen evolution performance of the electrocatalyst of the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere, 1cm multiplied by 1cm of foamed nickel/nickel sulfide/molybdenum disulfide hollow sphere composite material is directly used as a working electrode, a graphite rod electrode and a saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and 1.0M KOH is used as electrolyte. The scanning rate is 5mV s -1 The polarization curve of the electrocatalyst was tested at a current density of 50mA cm -2 The corresponding overpotential and Tafel slopes were 398mV and 85 mV/dec.
In conclusion, according to the nickel sulfide/molybdenum disulfide composite hollow spheres constructed on the foamed nickel, the hollow sphere structures grow on the holes of the conductive three-dimensional foamed nickel in situ, and the foamed nickel and the nickel sulfide/molybdenum disulfide hollow spheres form good connection, so that the stability and the conductivity of the material are improved, and the hollow spheres are mainly applied to the electrocatalytic oxygen evolution direction. The nickel sulfide and the molybdenum disulfide are compounded to form a hollow sphere structure, active sites are fully exposed, and the nickel sulfide and the molybdenum disulfide are cooperatively catalyzed to jointly enhance the electrocatalytic oxygen evolution performance. In the construction process of the nickel sulfide/molybdenum disulfide hollow sphere in-situ growth of the foamed nickel, the invention adopts a one-step hydrothermal method, has simple process and is beneficial to large-scale production.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material is characterized by comprising the following steps:
1) cutting the foamed nickel into blocks, washing to remove nickel oxide and grease, and drying to prepare blocky foamed nickel;
2) dissolving thioacetamide, anhydrous sodium molybdate and a nonionic triblock copolymer surfactant in deionized water to obtain a mixed solution, and putting the massive foam nickel prepared in the step 1) into the mixed solution to be fully and uniformly mixed at room temperature;
3) and (3) preserving the heat of the uniformly mixed solution obtained in the step 2) at 200 ℃ for 24 hours, washing and drying to obtain the foamed nickel in-situ growth nickel sulfide/molybdenum disulfide composite hollow sphere structure three-dimensional composite material.
2. The method for preparing the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material according to claim 1, wherein in the step 1), the nickel foam is cut into rectangular blocks.
3. The method for preparing the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material according to claim 2, wherein the rectangular nickel foam has the size of 2cm x 4cm, the thickness of 1.0mm and the pore diameter of 120 ppi.
4. The method for preparing the nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material by foam nickel in-situ growth according to claim 1, wherein in the step 1), acetone, hydrochloric acid, deionized water and ethanol are used for washing in sequence.
5. The method for preparing the nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material for in-situ growth of foamed nickel according to claim 1, wherein in the step 2), the mass ratio of thioacetamide, anhydrous sodium molybdate and the nonionic surfactant is 4:3: 7.
6. The method for preparing the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material according to claim 5, wherein the non-ionic surfactant is triblock copolymer L31, P123 or F127.
7. The method for preparing the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material according to claim 1, wherein in the step 3), the uniformly mixed solution is heated to 200 ℃ from room temperature at a rate of 10 ℃/min.
8. The method for preparing the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material according to claim 1, wherein in the step 2), the integrated foam is washed by deionized water and ethanol.
9. The nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material prepared by the method for preparing the nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material in situ grown from the foam nickel according to any one of claims 1 to 8 is characterized in that the nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material in situ grown from the foam nickel is porous/compact, the hollow spheres are uniformly distributed, and the diameter of the hollow spheres is 7 to 30 micrometers; the surface of the hollow sphere is composed of a plurality of rice-shaped particles with the length of about 100 nm; the thickness of the spherical shell of the hollow sphere is 200 nm-1 μm.
10. The use of the nickel foam in-situ growth nickel sulfide/molybdenum disulfide hollow sphere three-dimensional composite material of claim 9 in the preparation of an electrocatalyst.
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