CN114990608B - NiCoP two-dimensional ultrathin film with sub-nanometer thickness and preparation method thereof - Google Patents
NiCoP two-dimensional ultrathin film with sub-nanometer thickness and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a sub-nanometer-thickness NiCoP two-dimensional ultrathin film, which has the characteristics that the preparation method comprises the following steps: step 1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 A two-dimensional film; step 2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a sub-nano-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof.
Background
Electrocatalytic water splitting hydrogen production is considered one of the best ways to replace non-renewable energy sources. However, the current commercial electrocatalytic water splitting catalysts are still noble metal catalysts, which greatly increases the cost of electrocatalytic water splitting hydrogen production technology. The search for inexpensive non-noble metal catalysts as efficient electrocatalysts to replace noble metal catalysts has also become a key to commercial sustainable hydrogen production. In this regard, transition metal phosphide electrocatalysts may have greater potential as catalysts for electrocatalytic water decomposition because of their inherent metallic nature, which makes them more conductive than non-noble metal oxides, non-noble metal carbides, non-noble metal nitrides, and the like. In particular, the bimetallic phosphide has an electronic structure regulated by the mutual influence of unique electronic characteristics among different components, which can effectively regulate the adsorption and desorption of reactants by the electrocatalyst to improve the intrinsic activity, thereby showing better electrocatalytic activity.
The transition metal phosphide with proper phase structure and morphology structure can improve the efficiency of electrocatalytic water decomposition. For example, constructing a catalyst with a crystalline-amorphous phase can combine good conductivity of the crystalline phase with rich unsaturated coordination of the amorphous phase, which can increase the electrocatalytic reactivity. Compared with a bulk structure, the two-dimensional material with the sub-nanometer thickness not only can provide larger surface area to expose more active sites to enhance the intrinsic activity of the catalyst; and the thickness of the sub-nanometer level is favorable for the contact of the active site and the reactant, and the mass transfer and charge transfer efficiency is enhanced. However, the high surface energy possessed by two-dimensional materials having sub-nanometer thicknesses readily results in self-aggregation thereof. In particular, transition metal phosphides have an inherent triangular prism structure, which makes controlled synthesis of two-dimensional transition metal phosphides having nanometer or sub-nanometer thicknesses a great challenge. In recent years, the ultrasonic method has the advantages of simple operation, high synthesis efficiency and low cost, and provides a new strategy for synthesizing the two-dimensional material. The high-intensity ultrasonic wave can generate high-pressure shock wave and high-speed micro-jet flow to accelerate the movement speed of particles in the solution, so that the collision probability among the particles can be increased, the accumulation of the particles is effectively avoided, and conditions are created for the particles mutually collided in the solution to form a two-dimensional structure.
Disclosure of Invention
The invention aims to solve the problems and aims to provide a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof.
The invention provides a preparation method of a sub-nanometer-thickness NiCoP two-dimensional ultrathin film, which has the characteristics that the preparation method comprises the following steps: step 1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 A two-dimensional film; step 2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein, step 1 specifically includes the following steps: step 1-1, dissolving nickel chloride hexahydrate in an aqueous solution of cobalt chloride hexahydrate to obtain a first mixed solution; step 1-2, slowly adding a freshly prepared sodium borohydride solution dropwise into the first mixed solution under the action of ultrasonic waves to obtain a second mixed solution; step 1-3, repeatedly and rapidly washing the second mixed solution by deionized water and absolute ethyl alcohol to obtain NiCo (OH) with sub-nanometer-level thickness 2 A two-dimensional film.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein in the step 1-1, the mass ratio of the nickel chloride hexahydrate to the cobalt chloride hexahydrate is 2.5% -10%.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: in the step 1-2, the power of the ultrasonic wave is 0-650 watts.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein, step 2 specifically includes the following steps: step 2-1, niCo (OH) 2 The two-dimensional film and sodium hypophosphite are respectively arranged in two porcelain boats; step 2-2, placing a porcelain boat filled with sodium hypophosphite at an upper tuyere of a quartz tube in a CVD tube furnace, and filling NiCo (OH) 2 The porcelain boat of the two-dimensional film is arranged at the lower air opening; step 2-3, introducing inert gas into the CVD tube furnace; step 2-4, heating and preserving heat of the CVD tube furnace while keeping continuous introduction of inert gas; step 2-5, naturally cooling the CVD tube furnace to room temperature while keeping continuous introduction of inert gas; and 2-6, repeatedly and rapidly washing with deionized water and absolute ethyl alcohol, and freeze-drying to obtain the NiCoP two-dimensional film with the thickness of sub-nanometer level.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein, in the step 2-1, the mass of the sodium hypophosphite is 0.3-2 g.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein, in the step 2-3, the inert gas is any one of argon or nitrogen.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film provided by the invention can also have the following characteristics: wherein in the step 2-4, the temperature of heat preservation is 250-400 ℃ and the time of heat preservation is 1-5 hours.
The invention provides a NiCoP two-dimensional film, which has the following characteristics: the NiCoP two-dimensional film is prepared by the preparation method of the NiCoP two-dimensional ultrathin film with any sub-nanometer thickness.
The NiCoP two-dimensional film provided by the invention can also have the following characteristics: the NiCoP two-dimensional film is a two-dimensional structure with a thickness of sub-nanometer level.
Effects and effects of the invention
According to the preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film, which is provided by the invention, the preparation method comprises the following specific steps: step 1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 A two-dimensional film; step 2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained.
Therefore, the NiCoP two-dimensional film with the thickness of sub-nanometer level prepared by the method of ultrasonic wave induced aggregation and phase transformation has certain universality. The method can be popularized to other metals with hydroxide precipitation property and used for preparing composite nano materials.
In addition, the invention adopts simple and cheap raw materials as reactants, and has rich raw material reserves and low industrial cost.
Finally, the invention has simple process, mild preparation condition, convenient and simple product treatment and is suitable for medium-scale industrial production.
Drawings
FIG. 1 is NiCo (OH) with sub-nanometer scale thickness prepared in example 1 of the present invention 2 An SEM image of a two-dimensional film, wherein fig. 1 (a) is an SEM image of a product having an ultrasonic power of 0 watt-hour, fig. 1 (b) is an SEM image of a product having an ultrasonic power of 100 watt-hours, fig. 1 (c) is an SEM image of a product having an ultrasonic power of 300 watt-hours, fig. 1 (d) is an SEM image of a product having an ultrasonic power of 650 watt-hours, and fig. 1 (e) is an XRD image of a product having an ultrasonic power of 650 watt-hours;
FIG. 2 is an SEM image, an AFM image, an XRD image and an ED, respectively, of a two-dimensional film of NiCoP having a sub-nanometer thickness prepared in example 2 of the present inventionS diagram, wherein FIG. 2 (a 1 ) FIG. 2 (a) 2 ) SEM image and AFM image of the product obtained when the mass of nickel chloride hexahydrate was 2.1 mg, respectively, fig. 2 (b) 1 ) FIG. 2 (b) 2 ) SEM and AFM images of the product obtained when the mass of nickel chloride hexahydrate was 4.2 mg, respectively, fig. 2 (c) 1 ) FIG. 2 (c) 2 ) SEM and AFM images of the product obtained when the mass of nickel chloride hexahydrate was 8.3 mg, respectively, fig. 2 (d) 1 ) FIG. 2 (d) 2 ) Respectively SEM image and AFM image of the product of nickel chloride hexahydrate with a mass of 0 mg, fig. 2 (e) is XRD image of the prepared NiCoP two-dimensional thin film with a sub-nanometer level thickness, and fig. 2 (f) is EDS image of the prepared NiCoP two-dimensional thin film with a sub-nanometer level thickness;
FIG. 3 is an SEM image and an XRD pattern of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared in example 3 of the present invention, wherein FIG. 3 (a) is a product SEM image when the mass of sodium hypophosphite is 0.3 g, FIG. 3 (b) is a product SEM image when the mass of sodium hypophosphite is 0.5 g, FIG. 3 (c) is a product SEM image when the mass of sodium hypophosphite is 1.0 g, FIG. 3 (d) is a product SEM image when the mass of sodium hypophosphite is 1.5 g, FIG. 3 (e) is a product SEM image when the mass of sodium hypophosphite is 1.8 g, and FIG. 3 (f) is an XRD pattern of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared;
FIG. 4 is an SEM image and an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared in example 4 of the present invention, wherein FIG. 4 (a) is a SEM image of a product at a soak temperature of 250 degrees Celsius, FIG. 4 (b) is a SEM image of a product at a soak temperature of 280 degrees Celsius, FIG. 4 (c) is a SEM image of a product at a soak temperature of 300 degrees Celsius, FIG. 4 (d) is a SEM image of a product at a soak temperature of 230 degrees Celsius, FIG. 4 (e) is a SEM image of a product at a soak temperature of 380 degrees Celsius, FIG. 4 (f) is a SEM image of a product at a soak temperature of 400 degrees Celsius, and FIG. 4 (g) is an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared;
FIG. 5 is an SEM image and an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared in example 5 according to the present invention, wherein FIG. 5 (a) is a product SEM image at a holding time of 1 hour, FIG. 5 (b) is a product SEM image at a holding time of 2 hours, FIG. 5 (c) is a product SEM image at a holding time of 4 hours, FIG. 5 (d) is a product SEM image at a holding time of 5 hours, and FIG. 5 (e) is an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared;
FIG. 6 is an SEM image of a two-dimensional film of NiCoP obtained at a mass of 8.3 mg of nickel chloride hexahydrate in example 2 of the present invention.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the invention easy to understand, the following embodiment is used for specifically describing a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof by combining with the accompanying drawings.
Example 1
In this embodiment, a NiCo (OH) having a sub-nanometer thickness is provided 2 A two-dimensional film and a method for preparing the same.
NiCo (OH) having a sub-nanometer thickness according to this embodiment 2 The preparation method of the two-dimensional film comprises the following steps:
in step S1, 4.165 mg of nickel chloride hexahydrate was dissolved in 100 ml of an aqueous solution containing 83.3 mg of cobalt chloride hexahydrate.
Step S2, slowly adding 30 ml of freshly prepared sodium borohydride solution with the concentration of 13 millimoles dropwise under the action of ultrasonic power with different power, and continuously acting for 2 hours by ultrasonic waves. In this example, the ultrasonic power was 0 watt, 10 watt 0 watt, 300 watt, 650 watt, respectively.
And S3, centrifugally separating the precipitate, repeatedly cleaning the precipitate with deionized water and absolute ethyl alcohol, drying the precipitate in a freeze dryer for 48 hours, taking out the precipitate, and hermetically preserving the precipitate in an inert atmosphere.
FIG. 1 is NiCo (OH) with sub-nanometer scale thickness prepared in example 1 of the present invention 2 An SEM image of a two-dimensional film, wherein FIG. 1 (a) is an SEM image of a product having an ultrasonic power of 0 watt-hour, FIG. 1 (b) is an SEM image of a product having an ultrasonic power of 100 watt-hours, FIG. 1 (c) is an SEM image of a product having an ultrasonic power of 300 watt-hours, FIG. 1 (d) is an SEM image of a product having an ultrasonic power of 650 watt-hours, and FIG. 1 (e) is an ultrasonic power of 650 watt-hoursIs a XRD pattern of (C).
As shown in FIG. 1, FIGS. 1 (a) -1 (d) show NiCo (OH) with sub-nanometer thickness prepared under the action of different ultrasonic powers 2 SEM image of two-dimensional film. It can be seen that NiCo (OH) was prepared with the variation of the ultrasonic power 2 The morphology is obviously different, when the ultrasonic power is 0W, that is, the ultrasonic wave is not applied, the prepared NiCo (OH) 2 Is a sphere formed by two-dimensional film clusters; when the ultrasonic power is increased and the agglomerated spheres of the two-dimensional film are gradually unfolded, the prepared NiCo (OH) has the ultrasonic power of 650 watts 2 The degree of spread of the topography is best. By applying NiCo (OH) 2 X-ray diffraction (XRD) pattern analysis of (C) was carried out, it was observed that Cu (OH) appeared at 19.1 °, 32.6 °, 38.0 °, 51.5 °, 58.1 ° and 61.7 °, respectively 2 (001), (100), (011), (012), (110) and (111) crystal plane diffraction peaks corresponding to NiCo (OH) 2 PDF #74-1057 card of (f). Proved by NiCo (OH) 2 Is a successful synthesis of (a).
Example 2
In the embodiment, a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof are provided.
In this example, the CVD tube furnace is designated Chemical Vapor Deposition throughout. The tube furnace is mainly applied to industries such as metallurgy, glass, heat treatment, lithium battery anode and cathode materials, new energy, grinding tools and the like, and is professional equipment for measuring materials under certain air temperature conditions.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film comprises the following steps:
step S1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 The two-dimensional film specifically comprises the following steps:
in step S1-1, nickel chloride hexahydrate of different qualities was dissolved in 100 ml of an aqueous solution containing 83.3 mg of cobalt chloride hexahydrate, respectively. In this example, the mass ratio of nickel chloride hexahydrate to cobalt chloride hexahydrate was 0 mg, 2.1 mg, 4.2 mg, 8.3 mg, respectively, i.e., 0, 2.5%, 5.0%, 10%, respectively.
Step S1-2, under the action of 650 watts of ultrasonic power, slowly adding 30 milliliters of freshly prepared sodium borohydride solution with the concentration of 13 millimoles dropwise, and continuously acting for 2 hours by ultrasonic waves.
And S1-3, repeatedly cleaning the precipitate with deionized water and absolute ethyl alcohol after centrifugal separation, drying the precipitate in a freeze dryer for 48 hours, taking out, and hermetically preserving in an inert atmosphere.
Step S2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained, and the method specifically comprises the following steps:
step S2-1, 12 mg of NiCo (OH) prepared above was reacted with 2 And 1.5 g of sodium hypophosphite are respectively placed in two porcelain boats;
step S2-2, placing a porcelain boat filled with sodium hypophosphite at an upper air port of a quartz tube in the CVD tube furnace, and filling NiCo (OH) 2 The porcelain boat is arranged at the lower tuyere;
s2-3, introducing inert gas into the CVD tube furnace;
s2-4, keeping continuous introduction of inert gas, heating the CVD tube furnace from room temperature to 380 ℃ and preserving heat for 4 hours;
s2-5, taking out the product in the porcelain boat at the lower tuyere after the CVD tube furnace is naturally cooled to room temperature, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, drying the product in a freeze dryer for 48 hours, taking out the product, and sealing and preserving the product in an inert atmosphere.
FIG. 2 is an SEM image, an AFM image, an XRD image and an EDS image, respectively, of a two-dimensional film of NiCoP having a sub-nanometer thickness prepared in example 2 of the present invention, wherein FIG. 2 (a) 1 ) FIG. 2 (a) 2 ) SEM image and AFM image of the product obtained when the mass of nickel chloride hexahydrate was 2.1 mg, respectively, fig. 2 (b) 1 ) FIG. 2 (b) 2 ) SEM and AFM images of the product obtained when the mass of nickel chloride hexahydrate was 4.2 mg, respectively, fig. 2 (c) 1 ) FIG. 2 (c) 2 ) Respectively, nickel chloride hexahydrate with a mass of 8.3 mgSEM and AFM images of the product of (a) and (b) of fig. 2 (d 1 ) FIG. 2 (d) 2 ) SEM images and AFM images of the product of nickel chloride hexahydrate with a mass of 0 mg, respectively, fig. 2 (e) is an XRD image of the prepared NiCoP two-dimensional thin film with a sub-nanometer thickness, and fig. 2 (f) is an EDS image of the prepared NiCoP two-dimensional thin film with a sub-nanometer thickness.
As shown in fig. 2, fig. 2 (a) -2 (d) show SEM images and AFM images of NiCoP two-dimensional films with sub-nanometer scale thickness prepared when nickel chloride hexahydrate of different qualities was added. It can be seen that as the mass ratio of nickel chloride hexahydrate increases, the morphology spread of the NiCoP two-dimensional film increases. When the mass ratio of the nickel chloride hexahydrate is more than 2.5 percent (b and c graphs), the nickel chloride hexahydrate has no obvious influence on the morphology of the NiCoP two-dimensional film. As can be seen from AFM photographs, the average thickness of the prepared NiCoP two-dimensional films is less than 1 nanometer. By analyzing the results of the X-ray spectroscopy (EDS) of the two-dimensional film of NiCoP in FIG. 2 (e), it can be seen that the Ni element content varies. By analyzing fig. 2 (f) for the NiCoP two-dimensional thin film X-ray diffraction (XRD) pattern, it was observed that the (111), (201), (210), (300), (002), (211) crystal plane diffraction peaks corresponding to the PDF #13-0420 card of NiCoP at 40.99 °, 44.90 °, 47.58 °, 54.44 °, 54.74 °, 55.33 °, respectively. Successful synthesis of NiCoP was demonstrated.
Example 3
In the embodiment, a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof are provided.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film comprises the following steps:
step S1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 The two-dimensional film specifically comprises the following steps:
step S1-1, 4.165 mg of nickel chloride hexahydrate was dissolved in 100 ml of an aqueous solution containing 83.3 mg of cobalt chloride hexahydrate.
Step S1-2, under the action of 650 watts of ultrasonic power, slowly adding 30 milliliters of freshly prepared sodium borohydride solution with the concentration of 13 millimoles dropwise, and continuously acting for 2 hours by ultrasonic waves.
And S1-3, repeatedly cleaning the precipitate with deionized water and absolute ethyl alcohol after centrifugal separation, drying the precipitate in a freeze dryer for 48 hours, taking out, and hermetically preserving in an inert atmosphere.
Step S2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained, and the method specifically comprises the following steps:
step S2-1, 12 mg of NiCo (OH) prepared above was reacted with 2 Sodium hypophosphite with different quality is respectively placed in two porcelain boats. In this example, the mass of sodium hypophosphite was 0.3 g, 0.5 g, 1.0 g, 1.5 g, 2.0 g, respectively.
Step S2-2, placing a porcelain boat filled with sodium hypophosphite at an upper air port of a quartz tube in the CVD tube furnace, and filling NiCo (OH) 2 The porcelain boat is arranged at the lower air port.
And step S2-3, introducing inert gas into the CVD tube furnace.
And step S2-4, heating the CVD tube furnace from room temperature to 380 ℃ while keeping continuous feeding of inert gas, and preserving heat for 4 hours.
S2-5, taking out the product in the porcelain boat at the lower tuyere after the CVD tube furnace is naturally cooled to room temperature, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, drying the product in a freeze dryer for 48 hours, taking out the product, and sealing and preserving the product in an inert atmosphere.
FIG. 3 is an SEM image and an XRD pattern of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared in example 3 of the present invention, wherein FIG. 3 (a) is a product SEM image when the mass of sodium hypophosphite is 0.3 g, FIG. 3 (b) is a product SEM image when the mass of sodium hypophosphite is 0.5 g, FIG. 3 (c) is a product SEM image when the mass of sodium hypophosphite is 1.0 g, FIG. 3 (d) is a product SEM image when the mass of sodium hypophosphite is 1.5 g, FIG. 3 (e) is a product SEM image when the mass of sodium hypophosphite is 1.8 g, and FIG. 3 (f) is an XRD pattern of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared.
As shown in fig. 3, fig. 3 (a) -3 (e) show SEM images of NiCoP two-dimensional thin films with sub-nanometer scale thickness prepared when sodium hypophosphite of different quality was added. It can be seen that with the increase of the quality of sodium hypophosphite, no obvious effect is caused on the morphology of the NiCoP two-dimensional film. However, by analyzing the X-ray diffraction (XRD) pattern of the two-dimensional film of NiCoP, it was found that sodium hypophosphite of different mass had a great influence on the crystallinity of the two-dimensional film of NiCoP, and that the crystallinity of the two-dimensional film of NiCoP was the best when the mass of sodium hypophosphite was 1.5 g.
Example 4
In the embodiment, a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof are provided.
In this example, the CVD tube furnace is designated Chemical Vapor Deposition throughout. The tube furnace is mainly applied to industries such as metallurgy, glass, heat treatment, lithium battery anode and cathode materials, new energy, grinding tools and the like, and is professional equipment for measuring materials under certain air temperature conditions.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film comprises the following steps:
step S1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 The two-dimensional film specifically comprises the following steps:
step S1-1, 4.165 mg of nickel chloride hexahydrate was dissolved in 100 ml of an aqueous solution containing 83.3 mg of cobalt chloride hexahydrate.
Step S1-2, under the action of 650 watts of ultrasonic power, slowly adding 30 milliliters of freshly prepared sodium borohydride solution with the concentration of 13 millimoles dropwise, and continuously acting for 2 hours by ultrasonic waves.
And S1-3, repeatedly cleaning the precipitate with deionized water and absolute ethyl alcohol after centrifugal separation, drying the precipitate in a freeze dryer for 48 hours, taking out, and hermetically preserving in an inert atmosphere.
Step S2, niCo (OH) 2 The two-dimensional film phase is decomposed by heating and synchronously converted into NiCoP phase, and Ni with sub-nanometer level thickness is obtainedThe CoP two-dimensional film specifically comprises the following steps:
step S2-1, 12 mg of NiCo (OH) prepared above was reacted with 2 Respectively and 1.5 g of sodium hypophosphite are respectively placed in two porcelain boats.
Step S2-2, placing a porcelain boat filled with sodium hypophosphite at an upper air port of a quartz tube in the CVD tube furnace, and filling NiCo (OH) 2 The porcelain boat is arranged at the lower air port.
And step S2-3, introducing inert gas into the CVD tube furnace.
And step S2-4, heating the CVD tube furnace from room temperature to different temperatures respectively while keeping continuous introduction of inert gas, and preserving heat for 4 hours. In this embodiment, the temperature is raised to 250 degrees celsius, 280 degrees celsius, 300 degrees celsius, 330 degrees celsius, 380 degrees celsius, 400 degrees celsius, respectively.
S2-5, taking out the product in the porcelain boat at the lower tuyere after the CVD tube furnace is naturally cooled to room temperature, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, drying the product in a freeze dryer for 48 hours, taking out the product, and sealing and preserving the product in an inert atmosphere.
FIG. 4 is an SEM image and an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared in example 4 of the present invention, wherein FIG. 4 (a) is a SEM image of a product at a soak temperature of 250 degrees Celsius, FIG. 4 (b) is a SEM image of a product at a soak temperature of 280 degrees Celsius, FIG. 4 (c) is a SEM image of a product at a soak temperature of 300 degrees Celsius, FIG. 4 (d) is a SEM image of a product at a soak temperature of 230 degrees Celsius, FIG. 4 (e) is a SEM image of a product at a soak temperature of 380 degrees Celsius, FIG. 4 (f) is a SEM image of a product at a soak temperature of 400 degrees Celsius, and FIG. 4 (g) is an XRD image of a two-dimensional film of NiCoP having a sub-nanometer scale thickness prepared.
As shown in fig. 4, fig. 4 (a) -4 (f) show SEM images of NiCoP two-dimensional films with sub-nanometer scale thickness prepared at different soak temperatures. It can be seen that with the increase of the heat preservation temperature, no obvious effect is caused on the morphology of the NiCoP two-dimensional film. However, by analyzing the X-ray diffraction (XRD) pattern (g) of the two-dimensional film of NiCoP, it was found that different holding temperatures had a great influence on the crystallinity of the two-dimensional film of NiCoP, and that the crystallinity of the two-dimensional film of NiCoP was the best when the holding temperature was 380 ℃.
Example 5
In the embodiment, a sub-nanometer-thickness NiCoP two-dimensional ultrathin film and a preparation method thereof are provided.
In this example, the CVD tube furnace is designated Chemical Vapor Deposition throughout. The tube furnace is mainly applied to industries such as metallurgy, glass, heat treatment, lithium battery anode and cathode materials, new energy, grinding tools and the like, and is professional equipment for measuring materials under certain air temperature conditions.
The preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film comprises the following steps:
step S1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 The two-dimensional film specifically comprises the following steps:
step S1-1, 4.165 mg of nickel chloride hexahydrate was dissolved in 100 ml of an aqueous solution containing 83.3 mg of cobalt chloride hexahydrate.
Step S1-2, under the action of 650 watts of ultrasonic power, slowly adding 30 milliliters of freshly prepared sodium borohydride solution with the concentration of 13 millimoles dropwise, and continuously acting for 2 hours by ultrasonic waves.
And S1-3, repeatedly cleaning the precipitate with deionized water and absolute ethyl alcohol after centrifugal separation, drying the precipitate in a freeze dryer for 48 hours, taking out, and hermetically preserving in an inert atmosphere.
Step S2, niCo (OH) 2 The two-dimensional film phase is decomposed by heat and synchronously converted into a NiCoP phase, so that the NiCoP two-dimensional film with the thickness of sub-nanometer level is obtained, and the method specifically comprises the following steps:
step S2-1, 12 mg of NiCo (OH) prepared above was reacted with 2 Respectively and 1.5 g of sodium hypophosphite are respectively placed in two porcelain boats.
Step S2-2, placing a porcelain boat filled with sodium hypophosphite at an upper air port of a quartz tube in the CVD tube furnace, and filling NiCo (OH) 2 The porcelain boat is arranged at the lower air port.
And step S2-3, introducing inert gas into the CVD tube furnace.
And S2-4, heating the CVD tube furnace from room temperature to 380 ℃ while keeping continuous introduction of inert gas, and respectively preserving heat for different times. In this example, the incubation was performed for 1, 2, 4, and 5 hours, respectively.
S2-5, taking out the product in the porcelain boat at the lower tuyere after the CVD tube furnace is naturally cooled to room temperature, repeatedly cleaning the product with deionized water and absolute ethyl alcohol, drying the product in a freeze dryer for 48 hours, taking out the product, and sealing and preserving the product in an inert atmosphere.
Fig. 5 is an SEM image and an XRD image of a NiCoP two-dimensional thin film having a sub-nanometer scale thickness prepared in example 5 of the present invention, wherein fig. 5 (a) is an SEM image of a product at a soak time of 1 hour, fig. 5 (b) is an SEM image of a product at a soak time of 2 hours, fig. 5 (c) is an SEM image of a product at a soak time of 4 hours, fig. 5 (d) is an SEM image of a product at a soak time of 5 hours, and fig. 5 (e) is an XRD image of a NiCoP two-dimensional thin film having a sub-nanometer scale thickness prepared.
As shown in fig. 5, fig. 5 (a) -5 (d) show SEM images of NiCoP two-dimensional films with sub-nanometer scale thickness prepared at different soak times. It can be seen that with the increase of the heat preservation time, no obvious effect is caused on the morphology of the NiCoP two-dimensional film. However, by analyzing the X-ray diffraction (XRD) pattern (e) of the two-dimensional film of NiCoP, it was found that the different holding times had a great influence on the crystallinity of the two-dimensional film of NiCoP, and that the crystallinity of the two-dimensional film of NiCoP was the best when the holding time was 4 hours.
FIG. 6 is an SEM image of a two-dimensional film of NiCoP obtained at a mass of 8.3 mg of nickel chloride hexahydrate in example 2 of the present invention.
Effects and effects of the examples
According to the preparation method of the sub-nanometer-thickness NiCoP two-dimensional ultrathin film, which is related to the embodiment, the preparation method comprises the following specific steps: step 1, cobalt chloride hexahydrate and nickel chloride hexahydrate are used as raw materials, and NiCo (OH) with sub-nanometer-level thickness is prepared under the action of ultrasonic waves 2 A two-dimensional film; step 2, niCo (OH) 2 Two-dimensional film phase is decomposed by heating and converted synchronouslyFor the NiCoP phase, a two-dimensional film of NiCoP with a thickness on the sub-nanometer scale was obtained.
Therefore, the NiCoP two-dimensional film with the thickness of sub-nanometer level prepared by the method of ultrasonic wave induced aggregation and phase transformation has certain universality. The method can be popularized to other metals with hydroxide precipitation property and used for preparing composite nano materials.
In addition, the embodiment adopts simple and cheap raw materials as reactants, and has rich raw material reserves and low industrial cost.
Finally, the embodiment has simple process, mild preparation conditions, convenient and simple product treatment and is suitable for medium-scale industrial production.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (8)
1. A preparation method of a sub-nanometer-thickness NiCoP two-dimensional ultrathin film is characterized in that
The method comprises the following steps:
step 1, cobalt chloride hexahydrate and nickel chloride hexahydrate are taken as raw materials, and ultrasonic wave is carried out
Preparing a NiCo (OH) 2 two-dimensional film with a sub-nanometer level thickness under the action;
step 2, the NiCo (OH) 2 two-dimensional film phase is decomposed by heating and synchronously converted into
A NiCoP phase to obtain a NiCoP two-dimensional film with a thickness of sub-nanometer scale,
wherein, step 1 specifically includes the following steps:
step 1-1, dissolving nickel chloride hexahydrate in aqueous solution of cobalt chloride hexahydrate to obtain
To a first mixed solution;
step 1-2, slowly dropwise adding the first mixed solution under the action of ultrasonic waves
Adding a freshly prepared sodium borohydride solution to obtain a second mixed solution;
step 1-3, centrifugally separating the second mixed solution to obtain a precipitate, and
the precipitate is repeatedly and rapidly washed by deionized water and absolute ethyl alcohol to obtain the product with sub-nanometer
A two-dimensional film of NiCo (OH) 2 with a thickness in the order of meters,
the step 2 specifically comprises the following steps:
step 2-1, respectively placing the NiCo (OH) 2 two-dimensional film and sodium hypophosphite in two pairs
The porcelain boat is arranged in the porcelain boat;
step 2-2, placing the porcelain boat filled with the sodium hypophosphite in a CVD tube furnace for stone
Placing a porcelain boat provided with the NiCo (OH) 2 two-dimensional film at a lower air opening of an upper air opening of the English pipe;
step 2-3, introducing inert gas into the CVD tube furnace;
step 2-4, maintaining continuous introduction of the inert gas while maintaining the CVD tube
Heating and preserving heat in a furnace;
step 2-5, maintaining continuous introduction of the inert gas while maintaining the CVD tube
Naturally cooling the furnace to room temperature;
step 2-6, repeatedly and rapidly washing with deionized water and absolute ethyl alcohol, and freeze-drying to obtain
A two-dimensional film of NiCoP with a sub-nanometer thickness is obtained.
2. A sub-nanometer thickness NiCoP two-dimensional ultrathin film according to claim 1
The preparation method of (2) is characterized in that:
wherein in step 1-1, the nickel chloride hexahydrate is of a quality relative to cobalt chloride hexahydrate
The weight ratio is 2.5% -10%.
3. A sub-nanometer thickness NiCoP two-dimensional ultrathin film according to claim 1
The preparation method of (2) is characterized in that:
in the step 1-2, the power of the ultrasonic wave is 0-650 watts.
4. A sub-nanometer thickness NiCoP two-dimensional ultrathin film according to claim 1
The preparation method of (2) is characterized in that:
in the step 2-1, the mass of the sodium hypophosphite is 0.3-2 g.
5. A sub-nanometer thickness NiCoP two-dimensional ultrathin film according to claim 1
The preparation method of (2) is characterized in that:
in the step 2-3, the inert gas is any one of argon or nitrogen.
6. A sub-nanometer thickness NiCoP two-dimensional ultrathin film according to claim 1
The preparation method of (2) is characterized in that:
wherein in the step 2-4, the temperature of heat preservation is 250-400 ℃,
the heat preservation time is 1-5 hours.
7. A NiCoP two-dimensional film is characterized in that:
the NiCoP two-dimensional film is formed by the sub-nanometer thickness of any one of claims 1-6
The preparation method of the NiCoP two-dimensional ultrathin film is used for preparing the NiCoP two-dimensional ultrathin film.
8. The NiCoP two-dimensional film of claim 7 wherein:
the NiCoP two-dimensional film is of a two-dimensional structure with a thickness of sub-nanometer level.
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