CN114890474A - Superfine niobium-based nanocrystal/carbon nanosheet composite material and preparation method and application thereof - Google Patents
Superfine niobium-based nanocrystal/carbon nanosheet composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a superfine niobium-based nanocrystal/carbon nanosheet composite material, and a preparation method and application thereof. The composite nano material has a two-dimensional sheet structure with large size (>50 mu m) and composed of amorphous carbon and niobium-based compound, wherein 5-10nm superfine niobium pentoxide nano crystals or 10-20nm superfine niobium carbide nano crystals are embedded in a sheet layer. The niobium-gluconate precursor is obtained by reacting niobium hydroxide with gluconic acid, the precursor is directly carbonized, and the niobium-based compound nanocrystal/carbon nanosheet composite materials with different components and sizes can be prepared by changing the high-temperature calcination temperature and time. The invention has simple and convenient synthesis process, easily controlled reaction conditions and low cost, can be used in the fields of pseudo-capacitor super capacitor electrode materials, electrochemical catalytic materials, photocatalytic materials, electromagnetic wave absorption materials and the like, and has wide application value.
Description
Technical Field
The invention relates to the field of functional two-dimensional metal compound-carbon composite materials, in particular to a superfine niobium-based nanocrystal/carbon nanosheet composite material and a preparation method and application thereof.
Background
Two-dimensional nanostructured materials with ultra-thin thickness and large lateral dimensions have unique physical properties. Various scientific researches are carried out to widen the application field of the carbon nano-sheet and improve the application performance of the carbon nano-sheet. For example, non-metallic heteroatom doping is an effective method to enhance the electron donor properties of carbon nanoplates. Doping with heteroatom, and mixing with metal compounds such as: the compounding of the metal oxide, the metal nitride and the metal sulfide can endow the carbon nano-sheet with new dielectric, magnetic, catalytic, photoelectric and electrochemical performances.
The typical preparation method of the metal compound/carbon nanosheet composite material is a two-step process, which can be divided into the synthesis of the carbon nanosheets and the combination of the carbon nanosheets and the metal compound. The methods of making carbon nanoplatelets are commonly referred to as top-down and bottom-up strategies. The top-down method is a method of peeling or delaminating two-dimensional nano-platelets from their parent lamellar crystals by mechanical and chemical cleavage, but the yield is low and it is technically difficult to mass-produce. The bottom-up method is performed by applying a hard mask (NaCl, Mg (OH) 2 Silica, montmorillonite, etc.) or a soft template, or self-assembling and growing carbon precursors (block polymers, small organic molecules) to construct a two-dimensional carbon nanostructure. The bottom-up approach may provide more preparation strategy options than the top-down approach. However, removal of the template often requires a complicated process. In particular some hard templates that are tough require corrosive acids to etch. For bonding metal compounds and preparing carbon nanosheetsIn general, complicated production methods such as impregnation, precipitation, hydrothermal/solvothermal methods, and the like are used. Obviously, the two-step synthesis process is time-consuming and often leads to collapse of the two-dimensional nanostructure during template removal and metal compound binding. In addition, the above processes typically consume large amounts of expensive carbon-forming precursors, organic solvents, salts, corrosive acids. The complicated experimental condition control results in high production cost, and the non-environment-friendly preparation strategy brings huge environmental pressure to large-scale production. Therefore, the development of a simple and sustainable construction strategy for metal composite/carbon nanosheet composite is still an urgent task.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple and effective superfine niobium-based nanocrystal/carbon nanosheet composite material which can be used for large-scale production and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an ultrafine niobium-based nanocrystal/carbon nanosheet composite material comprises the following steps:
preparing a fresh niobium hydroxide suspension: adding ammonium niobate oxalate hydrate into ultrapure water, stirring to obtain ammonium niobate oxalate solution, adding ammonia water into the ammonium niobate oxalate solution to adjust the pH value, and obtaining fresh niobium hydroxide suspension;
preparing a niobium-gluconate precursor: adding a gluconic acid solution into the fresh niobium hydroxide suspension, heating and stirring until the solution becomes clear to obtain a niobium-gluconate precursor aqueous solution, adding the niobium-gluconate precursor aqueous solution into absolute ethyl alcohol, separating and drying to obtain a niobium-gluconate precursor;
preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material: and carbonizing the dried niobium-gluconate precursor to obtain the superfine niobium-based nanocrystal/carbon nanosheet composite material.
Further, the pH value of the ammonium niobate oxalate solution is adjusted to be more than 7.
Further, the molar ratio of ammonium niobate oxalate hydrate to gluconic acid is (5-7): 1.
Further, the mass fraction of the gluconic acid in the gluconic acid solution is 49-53%.
Further, the temperature of the heating and stirring is 80-90 ℃.
Further, the carbonization treatment conditions are as follows: heating to 600-1200 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 1-4h, and then naturally cooling.
Further, protective gas with the flow rate of 150-.
An ultra-fine niobium-based nanocrystal/carbon nanoplatelet composite as prepared by the method of claim, wherein the mass content of niobium-based nanocrystals in the composite is 38.5-39.9%.
Further, in the composite material, the niobium-based nanocrystal size is as follows: 5-20nm, two-dimensional sheet structure size>50 μm, specific surface area: 277-362cm 3 (g) a micropore surface area of 111- 2 (ii)/g; the total pore volume is 0.19-0.24cm 3 Per g, wherein the pore volume of the micropores is 0.05-0.14cm 3 /g。
The application of the superfine niobium-based nanocrystal/carbon nanosheet composite material is applied to the field of pseudo-capacitor supercapacitor electrode materials, electrochemical catalytic materials, photocatalytic materials or electromagnetic wave absorption materials.
In the invention, the preparation principle of the superfine niobium-based nanocrystal/carbon nanosheet composite material is as follows: as shown in fig. 1, niobium-gluconate precursor, ultra-fine niobium-based nanocrystal/carbon nanosheet composite material is obtained by reacting niobium hydroxide with gluconic acid through direct carbonization. The species and size of the niobium-based compound nanocrystals can be adjusted by adjusting the calcination temperature and time during the carbonization process. During the carbonization process, pentavalent niobium ions in the niobium-gluconate precursor are separated from gluconate root to form niobium pentoxide and carbon skeleton respectively. In the high-temperature calcination process, the carbon matrix can form in-situ limited domain effect on the niobium pentoxide nanocrystal and inhibit the unlimited agglomeration growth of the niobium pentoxide nanocrystal, so that the size of the obtained niobium pentoxide nanocrystal can be maintained below 20nm to form the superfine nanocrystal. The carbon skeleton gradually reduces the niobium pentoxide nanocrystals to form niobium carbide nanocrystals as the calcination temperature is increased. In addition, at the initial stage of the carbonization process, the niobium-gluconate precursor can later enable the composite material to obtain a large-size two-dimensional planar structure through a unique self-foaming behavior.
Pseudo-capacitance supercapacitor electrode material: the super capacitor is considered to be an efficient and environment-friendly device due to the characteristics of fast charge and discharge, simple energy storage process, high power density, long service life and the like. Orthorhombic niobium pentoxide (T-Nb) 2 O 5 ) Has a density of 200mAh g -1 The high theoretical capacity of the electrode is a promising pseudo-capacitance super capacitor electrode material. T-Nb 2 O 5 A large number of hollow octahedral sites exist between the (001) surfaces, which is beneficial to the intercalation reaction of solid-phase ion diffusion and generates a special insertion-removal pseudocapacitance. The superfine niobium pentoxide nanocrystal/carbon nanosheet composite material can obtain excellent pseudocapacitance capacity and excellent conductivity, and is very suitable for being used as a pseudocapacitance supercapacitor electrode material.
Electrochemical catalytic material: niobium pentoxide (Nb) 2 O 5 ) The conductivity was about: 3.4X 10 -6 S/cm, niobium carbide (NbC) conductivity is about: 2.8X 10 -6 S/cm, the two niobium-based compounds have good electron transfer capacity, can be used as active components to be combined with reactants in electrochemical catalysis to promote the progress of electron transfer reaction, and the superfine crystal size can enable the niobium-based compounds to expose more chemical reaction active surfaces and increase reaction contact active sites. In addition, the carbon loading of the ultra-fine niobium-based compound can improve the conductivity of the material and the structural stability in chemical reaction. In addition, niobium pentoxide and niobium carbide are hardly compatible with most of acid and alkali solutions, have good acid and alkali stability and can exist stably in the catalytic reaction process. The superfine niobium-based nanocrystal/carbon nanosheet composite material can be applied to electrocatalysis of lithium-sulfur batteries, N catalytic reduction and the likeCan be applied in chemical fields.
Photocatalytic material: niobium pentoxide (Nb) 2 O 5 ) Is a typical non-toxic solid oxide with strong redox ability and unique Lewis Acid Site (LAS) and Bronsted Acid Site (BAS). Nb 2 O 5 The application range of (2) is expanded to the photocatalytic conversion of waste plastics, the activation of hydrocarbons, CO 2 And selective conversion of amines and alcohols. In addition, NbC also has some photocatalytic activity. The niobium-based compound with the superfine size in the superfine niobium-based nanocrystal/carbon nanosheet composite material can have higher catalytic activity for measurement and has great advantages in photocatalysis.
Electromagnetic wave absorbing material: niobium pentoxide and niobium carbide have dielectric properties, and the superfine niobium-based nanocrystal/carbon nanosheet composite material can generate charge transfer and accumulation at a crystal particle and carbon skeleton heterogeneous interface in an electromagnetic field, because the niobium-based nanocrystal and the carbon skeleton in the composite material have different electronic energy band structures and dielectric constants. The movement of the collective interface dipole amplifies the response to the incident electromagnetic field, thereby enhancing microwave absorption properties. The superfine niobium-based nanocrystal/carbon nanosheet composite material can realize excellent electromagnetic wave absorbing performance and has great application advantages in the field of electromagnetic wave absorbing materials.
Compared with the prior art, the invention has the following advantages:
(1) the preparation route is simple and convenient, and industrial scale production can be carried out: reacting freshly prepared niobium hydroxide with a gluconic acid solution to obtain niobium-gluconate, separating and drying a niobium-gluconate precursor, and carbonizing to obtain the superfine niobium-based nanocrystal/carbon nanosheet composite material; the preparation of the precursor is based on simple acid-base neutralization reaction, the preparation process is easy to realize large-scale production, and the formation of the nanocrystal and the formation of the macroscopic two-dimensional sheet structure are performed spontaneously in the carbonization process, so that compared with other preparation methods, the technical path greatly reduces the difficulty in preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material;
(2) the preparation of the macroscopic two-dimensional sheet structure of the superfine niobium-based nanocrystal/carbon nanosheet composite material is stable; the size of the niobium-based nanocrystal can be controlled, and the size of the niobium-based nanocrystal can be controlled by changing the high-temperature calcination temperature and the retention time in the carbonization process; the composition of the niobium-based nanocrystal is controllable and can be regulated and controlled by changing the high-temperature calcination temperature in the carbonization process;
(3) the prepared superfine niobium-based nanocrystal/carbon nanosheet composite material has a high specific surface area and a large number of superfine nanocrystal load characteristics, and has great application value in the fields of pseudo-capacitor supercapacitor electrode materials, electrochemical catalytic materials, photocatalytic materials, electromagnetic wave absorption materials and the like.
Drawings
FIG. 1 is a schematic diagram of the preparation principle of the present invention;
FIG. 2 is an XRD spectrum of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite Nb-800-2 prepared in example 1;
FIG. 3 is a scanning electron microscope image and a projection electron microscope image of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite Nb-800-2 prepared in example 1;
FIG. 4 is a graph of the reflection loss performance of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite Nb-800-2 prepared in example 1;
FIG. 5 is an XRD pattern of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite Nb-1200-2 prepared in example 5;
fig. 6 is a scanning electron microscope image and a projection electron microscope image of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite Nb-1200-2 prepared in example 5.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
A preparation method of an ultrafine niobium-based nanocrystal/carbon nanosheet composite material comprises the following steps:
preparing a fresh niobium hydroxide suspension: adding ammonium niobate oxalate hydrate into ultrapure water, stirring to obtain ammonium niobate oxalate solution, adding ammonia water into the ammonium niobate oxalate solution to adjust the pH value to be more than 7, and obtaining fresh niobium hydroxide suspension;
preparing a niobium-gluconate precursor: adding a gluconic acid solution into the fresh niobium hydroxide suspension, heating and stirring until the solution becomes clear to obtain a niobium-gluconate precursor aqueous solution, adding the niobium-gluconate precursor aqueous solution into absolute ethyl alcohol, separating and drying to obtain a niobium-gluconate precursor; the molar ratio of ammonium niobate oxalate hydrate to gluconic acid is (5-7):1, preferably 6: 1. The mass fraction of the gluconic acid in the gluconic acid solution is 49-53%. The temperature of the heating and stirring is 80 to 90 ℃, preferably 85 ℃.
Preparing an ultrafine niobium-based nanocrystal/carbon nanosheet composite material: and carbonizing the dried niobium-gluconate precursor to obtain the superfine niobium-based nanocrystal/carbon nanosheet composite material. The carbonization conditions were: heating to 600-1200 ℃ at the heating rate of 3 ℃/min, preferably 800 ℃, keeping the temperature for 1-4h, and then naturally cooling. Protective gas with the flow rate of 150-.
The mass content of the niobium-based nanocrystal in the composite material is 38.5-39.9%. The niobium-based nanocrystals had a size of: 5-20nm, two-dimensional sheet structure size>50 μm, specific surface area: 277-362cm 3 (g) a micropore surface area of 111- 2 (ii)/g; the total pore volume is 0.19-0.24cm 3 Per g, wherein the pore volume of the micropores is 0.05-0.14cm 3 (ii) in terms of/g. The composite material is applied to the field of pseudo-capacitor supercapacitor electrode materials, electrochemical catalytic materials, photocatalytic materials or electromagnetic wave absorption materials.
Example 1
The preparation method of the superfine niobium-based nanocrystal/carbon nanosheet composite material Nb-800-2 comprises the following specific preparation steps:
(1) preparing a fresh niobium hydroxide suspension:
weighing 24.71g of ammonium niobate oxalate hydrate, adding the weighed ammonium niobate oxalate hydrate into 60ml of ultrapure water, stirring to obtain an ammonium niobate oxalate solution, adding 25 mass percent of ammonia water into the ammonium niobate oxalate solution to adjust the pH value to be more than 7, and hydrolyzing niobium ions in the solution to obtain a fresh niobium hydroxide suspension;
(2) preparing a niobium-gluconate precursor:
adding 188g of 49-53% gluconic acid solution in mass fraction into the obtained fresh niobium hydroxide suspension, heating and stirring in a water bath at 85 ℃ until the solution becomes clear to obtain a niobium-gluconate precursor aqueous solution, adding the niobium-gluconate precursor aqueous solution into absolute ethyl alcohol, separating and drying to obtain a niobium-gluconate precursor;
(3) preparing an ultrafine niobium-based nanocrystal/carbon nanosheet composite material:
carbonizing the dried niobium-gluconate precursor, wherein the specific carbonizing conditions are as follows: heating to 800 ℃ at a heating rate of 3 ℃/min in a high-temperature tube furnace, keeping for 2h, then naturally cooling to room temperature, wherein in the carbonization treatment process, protective gas with a flow rate of 200mL/min is used as high-purity nitrogen gas, so that the superfine niobium-based nanocrystal/carbon nanosheet composite material is obtained, and is marked as Nb-800-2, wherein 800 refers to the calcination retention temperature in the carbonization process, and 2 refers to the calcination retention time in the carbonization process, and the unit is h.
Fig. 2 is an XRD spectrum of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite material Nb-800-2 prepared in this example, and the niobium-based nanocrystals obtained are orthorhombic niobium pentoxide under the condition of being treated at a carbonization temperature of 800 ℃ for two hours.
FIG. 3a is a scanning electron microscope image of Nb-800-2, which can be seen to have a larger size (diameter)>50 μm) of a two-dimensional sheet structure; FIG. 3b is a projection electron microscope image of Nb-800-2, which shows that ultrafine niobium pentoxide nanocrystals with a size of about 5nm are uniformly dispersed in the Nb-800-2 skeleton. In Nb-800-2, the mass content of the superfine niobium pentoxide nanocrystal is 39.9 percent. The BET specific surface area of Nb-800-2 is 362m 2 Per g, wherein the micropore surface area is 339m 2 (ii)/g; the total pore volume is 0.19cm 3 Per g, wherein is microPore volume of 0.14cm 3 /g。
FIG. 4 is a reflection loss performance diagram of an ultra-fine niobium-based nanocrystal/carbon nanosheet composite material Nb-800-2 applied to the field of electromagnetic wave absorbing materials, wherein the Nb-800-2 has a two-dimensional lamellar structure and can enhance the scattering loss of electromagnetic waves in materials, meanwhile, the dielectric ultra-fine niobium pentoxide nanocrystal inside the Nb-800-2 can enhance the dielectric loss, the obtained Nb-800-2 and paraffin are mixed according to a mass ratio of 4:6 and are subjected to compression molding, an electromagnetic wave frequency band reflectivity test of 2-18GHz is carried out by a coaxial method, and the Nb-800-2 shows excellent electromagnetic wave absorbing performance with the maximum reflection loss of-80.8 dB (the thickness is 2.76 mm).
Example 2
The preparation method of the superfine niobium-based nanocrystal/carbon nanosheet composite material Nb-600-2 comprises the following specific preparation steps:
the difference from the embodiment 1 is that: the calcination retention temperature in the carbonization process in the step (3) is changed to 600 ℃.
Example 3
The preparation method of the superfine niobium-based nanocrystal/carbon nanosheet composite material Nb-700-1 comprises the following specific preparation steps:
the difference from the embodiment 1 is that: in the step (3), the calcination retention temperature in the carbonization process is changed to 700 ℃, and the calcination retention time in the carbonization process is changed to 1 h.
Example 4
The preparation method of the superfine niobium-based nanocrystal/carbon nanosheet composite material Nb-800-4 comprises the following specific preparation steps:
the difference from the embodiment 1 is that: the calcination residence time in the carbonization process in the step (3) is changed to 4 h.
Example 5
The preparation method of the superfine niobium-based nanocrystal/carbon nanosheet composite material Nb-1200-2 comprises the following specific preparation steps:
the difference from the embodiment 1 is that: the calcination retention temperature in the carbonization process in the step (3) is changed to 1200 ℃.
Fig. 5 is an XRD spectrum of the ultra-fine niobium-based nanocrystal/carbon nanosheet composite material Nb-1200-2 prepared in this example, and the niobium-based nanocrystals obtained are orthorhombic niobium carbide when treated at a carbonization temperature of 1200 ℃ for two hours.
FIG. 6a is a scanning electron microscope image of Nb-1200-2, which can be seen to have a larger size (diameter)>50 μm) of a two-dimensional sheet structure; FIG. 6b is a projection electron microscope image of Nb-1200-2, which shows that ultrafine niobium carbide nanocrystals with a size of about 20nm are uniformly dispersed in the Nb-1200-2 skeleton. In Nb-1200-2, the content of the superfine niobium carbide nano-crystal is 38.5 percent. The BET specific surface area of Nb-1200-2 is 277m 2 Per g, wherein the micropore surface area is 110m 2 (ii)/g; the total pore volume is 0.24cm 3 Per g, wherein the pore volume of the micropores is 0.05cm 3 /g。
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a superfine niobium-based nanocrystal/carbon nanosheet composite material is characterized by comprising the following steps:
preparing a fresh niobium hydroxide suspension: adding ammonium niobate oxalate hydrate into water, stirring to obtain ammonium niobate oxalate solution, and adjusting the pH value to obtain fresh niobium hydroxide suspension;
preparing a niobium-gluconate precursor: adding a gluconic acid solution into the fresh niobium hydroxide suspension, heating and stirring until the solution becomes clear to obtain a niobium-gluconate precursor aqueous solution, adding the niobium-gluconate precursor aqueous solution into absolute ethyl alcohol, separating and drying to obtain a niobium-gluconate precursor;
preparing an ultrafine niobium-based nanocrystal/carbon nanosheet composite material: and carbonizing the dried niobium-gluconate precursor to obtain the superfine niobium-based nanocrystal/carbon nanosheet composite material.
2. The method for preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1, wherein the pH of the ammonium niobate oxalate solution is adjusted to be greater than 7.
3. The method for preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1, wherein the molar ratio of ammonium niobate oxalate hydrate to gluconic acid is (5-7): 1.
4. The method for preparing the ultra-fine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1, wherein the gluconic acid solution comprises 49-53% of gluconic acid by mass.
5. The method for preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1, wherein the heating and stirring temperature is 80-90 ℃.
6. The method for preparing the superfine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1, wherein the carbonization conditions are as follows: heating to 600-1200 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 1-4h, and then naturally cooling.
7. The method for preparing the ultra-fine niobium-based nanocrystal/carbon nanosheet composite material as claimed in claim 1 or 6, wherein the protective gas with a flow rate of 150-250mL/min is introduced during the carbonization treatment, and the protective gas is high-purity nitrogen.
8. An ultra-fine niobium-based nanocrystal/carbon nanoplatelet composite prepared according to the method of any of claims 1 to 7, wherein the mass content of niobium-based nanocrystals in the composite is 38.5 to 39.9%.
9. The ultra-fine niobium-based nanocrystal/carbon nanosheet composite of claim 8, wherein the niobium-based nanocrystals have a size of: 5-20nm, two-dimensional sheet structure size>50 μm, specific surface area: 277-362cm 3 (g) a micropore surface area of 111- 2 (ii)/g; the total pore volume is 0.19-0.24cm 3 Per g, wherein the pore volume of the micropores is 0.05-0.14cm 3 /g。
10. The application of the superfine niobium-based nanocrystal/carbon nanosheet composite material as defined in claim 8 or 9, wherein the composite material is applied to the field of pseudo-capacitor supercapacitor electrode materials, electrochemical catalytic materials, photocatalytic materials or electromagnetic wave absorption materials.
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