CN109603697B - A kind of nano-carbon hybrid aerogel and its preparation method and application - Google Patents
A kind of nano-carbon hybrid aerogel and its preparation method and application Download PDFInfo
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Abstract
本发明提供了一种纳米碳混杂气凝胶的制备方法，属于气凝胶技术领域。本发明将FL‑CNs与导电性纳米碳材料(碳纳米管)混杂，制备出三维多孔高导电率的超轻纳米碳混杂气凝胶，制得的气凝胶在电化学储能方面，可用作高导电率储能器件的电极；在催化特性方面，既可直接作为催化剂使用，又可通过官能团化或负载功能性纳米粒子，作为催化剂载体，有效提高催化作用，由于高比表面积和高氮活性点，使得该材料催化效率高，能有效降低贵金属催化剂的用量；同时，还用于高端隔热保温系统等。
The invention provides a preparation method of nano-carbon hybrid aerogel, which belongs to the technical field of aerogel. The invention mixes FL-CNs with conductive nano carbon materials (carbon nanotubes) to prepare three-dimensional porous and high-conductivity ultra-light nano carbon mixed aerogels, and the prepared aerogels can be used in electrochemical energy storage. It is used as an electrode for high-conductivity energy storage devices; in terms of catalytic properties, it can be used directly as a catalyst, and can be used as a catalyst carrier by functionalizing or loading functional nanoparticles to effectively improve the catalytic effect. Due to the high specific surface area and high Nitrogen active points make the material high catalytic efficiency, which can effectively reduce the amount of precious metal catalysts; at the same time, it is also used in high-end thermal insulation systems, etc.
Description
Technical Field
The invention belongs to the technical field of aerogel preparation, and particularly relates to a nano-carbon hybrid aerogel and a preparation method and application thereof.
Background
The term "nitrogen carbide" refers to graphite phase nitrogen carbide (g-CN), which is a graphene-like two-dimensional sheet-layered polymer semiconductor material composed of nitrogen and carbon elements and having a nitrogen-to-carbon atomic ratio > 1. Cavities exist in the material layer, and the structure of the cavities is different from that of graphene with a complete carbon layer structure and nitrogen-doped graphene. The nitrogen carbide has adjustable band gap and excellent light absorption performance, a cavity is formed in the nitrogen carbide layer due to the difference of chemical valence states of carbon and nitrogen, a host/object interaction reaction can be initiated by nitrogen lone pair electrons or NH functional groups arranged in the cavity, and the nitrogen carbide has wide application prospects in the fields of charge storage, ion diffusion, photocatalysis and the like.
The single-layer or few-layer carbon nitride nanosheets (FL-CNs) have outstanding photocatalytic performance, and become an emerging two-dimensional layered material. The two-dimensional layered material prepared in the prior art has the problem of low photocatalytic performance.
Disclosure of Invention
In view of the above, the present invention aims to provide a kind of nano carbon hybrid aerogel, and a preparation method and an application thereof. The nano carbon hybrid aerogel prepared by the preparation method provided by the invention has a three-dimensional network structure and excellent catalytic performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nano carbon hybrid aerogel, which comprises the following steps:
mixing metal sodium with an organic solvent containing sodium naphthalene under anhydrous and anaerobic conditions to obtain an electronic solution containing sodium counter ions;
mixing part of the electron solution containing sodium counter ions with the carbon nano tube to obtain a polyanion solution of the carbon nano tube;
mixing the rest electronic solution containing sodium counter ions with the nitrogen carbide to obtain a polyanionic solution of the nitrogen carbide;
and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene for cross-linking reaction to obtain the nano carbon mixed aerogel.
Preferably, the organic solvent is anhydrous dimethylacetamide, dimethylformamide or liquid ammonia.
Preferably, the molar ratio of sodium ions to carbon nanotubes in the partial electron solution containing sodium counter ions is 1: 4-100.
Preferably, the molar concentration of sodium ions in the part of the electronic solution containing sodium counter ions is 0.01-0.1 mol/L.
Preferably, the molar ratio of sodium ions to nitrogen carbide in the residual electron solution containing sodium counter ions is 1: 2-16.
Preferably, the molar concentration of sodium ions in the residual electron solution containing sodium counter ions is 0.006-0.06 mol/L.
Preferably, the molar ratio of the sum of sodium ions in the carbon nanotube polyanion solution and the nitrogen carbide polyanion solution to diiodobenzene is 1: 1.
Preferably, the time of the crosslinking reaction is 15min to 24 h.
The invention also provides the nano carbon hybrid aerogel prepared by the preparation method in the technical scheme.
The invention also provides the application of the nano carbon hybrid aerogel in the technical scheme in the field of electrocatalysis.
The invention provides a preparation method of nano-carbon hybrid aerogel, which comprises the following steps of mixing metal sodium with an organic solvent containing sodium naphthalene under the anhydrous and oxygen-free conditions to obtain an electronic solution containing sodium counter ions; mixing part of the electron solution containing sodium counter ions with the carbon nano tube to obtain a polyanion solution of the carbon nano tube; mixing the rest electronic solution containing sodium counter ions with the nitrogen carbide to obtain a polyanionic solution of the nitrogen carbide; and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene for cross-linking reaction to obtain the nano carbon mixed aerogel. The FL-CNs and the conductive nano carbon material (carbon nano tube) are mixed to prepare the three-dimensional porous high-conductivity ultra-light nano carbon mixed aerogel, and the prepared aerogel can be used as an electrode of a high-conductivity energy storage device in the aspect of electrochemical energy storage; in the aspect of catalytic characteristics, the material can be directly used as a catalyst, can be used as a catalyst carrier through functionalization or loading of functional nanoparticles, and can effectively improve the catalytic action; meanwhile, the heat insulation and preservation system is also used for high-end heat insulation and preservation systems and the like.
Description of the drawings:
fig. 1 is a spectrum of a nano carbon hybrid aerogel prepared in example 1, wherein (a) is an SEM spectrum, (b) is an SEM spectrum of a catalyst prepared by using the nano carbon hybrid aerogel prepared in example 1 as a catalyst carrier, and (c) is a distribution graph of an average particle size and a size of a nano platinum catalyst;
FIG. 2 is a current density curve of a platinum catalyst in an oxygen reduction reaction overvoltage interval of a nitrogen carbide, a reduced graphene oxide and nanocarbon mixed aerogel carrier and a platinum/carbon catalyst carrier;
fig. 3 is an optical photograph of the nanocarbon hybrid aerogel prepared in example 1;
fig. 4 is a high resolution SEM spectrum of the nanocarbon hybrid aerogel prepared in example 1;
fig. 5 is a plot of void distribution versus specific surface area for the nanocarbon hybrid aerogel prepared in example 1;
fig. 6 is a graph of conductivity versus raman spectrum defects of the nanocarbon hybrid aerogel prepared in example 1;
fig. 7 is an energy storage characteristic curve of the nanocarbon hybrid aerogel prepared in the embodiment, which is used for an energy storage device.
Detailed Description
The invention provides a preparation method of a nano carbon hybrid aerogel, which comprises the following steps:
mixing metal sodium with an organic solvent containing sodium naphthalene under anhydrous and anaerobic conditions to obtain an electronic solution containing sodium counter ions;
mixing part of the electron solution containing sodium counter ions with the carbon nano tube to obtain a polyanion solution of the carbon nano tube;
mixing the rest electronic solution containing sodium counter ions with the nitrogen carbide to obtain a polyanionic solution of the nitrogen carbide;
and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene for cross-linking reaction to obtain the nano carbon mixed aerogel.
The invention mixes metal sodium with organic solvent containing sodium naphthalene under anhydrous and anaerobic condition to obtain the electronic solution containing sodium counter ion. In the present invention, the organic solvent is preferably anhydrous dimethylacetamide, dimethylformamide or liquid ammonia. The electronic solution containing sodium counter ions prepared by the method can form polyanionic electrolyte of carbon nano tubes or nitrogen carbide by utilizing a spontaneous static stripping process, reduces the damage of other chemical (oxidation stripping and the like) or physical stripping (ultrasonic dispersion and the like) modes to the carbon nano tubes and the nitrogen carbide, keeps the monodispersed state of the material, prevents the influence of a crosslinking process on the specific surface area and the pore morphology of the material, and avoids the reagglomeration or the stacking of the stripped carbon nano tubes and the nitrogen carbide component material.
The concentration of sodium naphthalene in the sodium naphthalene-containing organic solvent is not particularly limited in the present invention.
After the electronic solution containing the sodium counter ions is obtained, part of the electronic solution containing the sodium counter ions is mixed with the carbon nano tubes to obtain the polyanion solution of the carbon nano tubes. In the invention, the molar ratio of sodium ions to carbon nanotubes in the partial sodium counter ion-containing electronic solution is preferably 1: 4-100, and more preferably 1: 10-12.
In the invention, the molar concentration of sodium ions in the partial electron solution containing sodium counter ions is preferably 0.01-0.1 mol/L, and more preferably 0.025-0.043 mol/L. In the mixing process, alkali metal ion sodium ions are driven to be rapidly transferred to the gap position from the charge transfer agent-naphthol, the obtained polyanion electrolyte of the carbon nano tube can be spontaneously dissolved in an organic solvent, and a highly dispersed and high-concentration solution is formed by controlling the charge quantity carried by a framework (an electronic solution containing sodium counter ions) of the component material.
In the invention, the concentration of the carbon nano tube in the carbon nano tube polyanion solution is preferably 0.5-6.5 mg/mL, and more preferably less than or equal to 2 mg/mL.
In the present invention, the diameter of the carbon nanotubes is preferably less than 50nm, and the raman G/D ratio of the carbon nanotubes is preferably > 100. In the present invention, the carbon nanotube is preferably a single-walled carbon nanotube. The source of the carbon nanotubes in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
After the electronic solution containing sodium counter ions is obtained, the remaining electronic solution containing sodium counter ions is mixed with the nitrogen carbide to obtain the polyanionic solution of the nitrogen carbide. In the invention, the molar ratio of sodium ions to nitrogen carbide in the residual electron solution containing sodium counter ions is preferably 1: 2-16, more preferably 1: 5-8, and most preferably 1: 7.1.
In the invention, the molar concentration of sodium ions in the residual electron solution containing sodium counter ions is preferably 0.006-0.06 mol/L, more preferably 0.012-0.020 mol/L, and most preferably 0.015 mol/L. In the mixing process, alkali metal ion sodium ions are driven to be rapidly transferred to gap positions from a charge transfer agent-naphthol, the obtained nitrogen carbide polyanion electrolyte can be spontaneously dissolved in an organic solvent, and a highly dispersed and high-concentration solution is formed by controlling the charge quantity carried by a component material framework (an electronic solution containing sodium counter ions).
In the invention, the concentration of the carbonized nitrogen in the carbonized nitrogen polyanion solution is preferably 0.5-4 mg/mL, and more preferably less than or equal to 3.5 mg/mL.
In the present invention, the nitrogen carbide is preferably a highly crystalline lamellar structure nitrogen carbide, and the nitrogen to carbon atomic ratio in the carbon nitride is preferably > 1. In the invention, the diameter of the nitrogen carbide is preferably 50-100 nanometers. The source of the nitrogen carbide in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
After the carbon nano tube polyanion solution and the nitrogen carbide polyanion solution are obtained, the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene are mixed for cross-linking reaction, and the nano carbon mixed aerogel is obtained.
In the present invention, the molar ratio of the sum of sodium ions in the carbon nanotube polyanion solution and the nitrogen carbide polyanion solution to diiodobenzene is preferably 1: 1.
In the invention, the time of the crosslinking reaction is preferably 15 min-24 h, and the temperature of the crosslinking reaction is preferably room temperature, and no additional heating or cooling is required.
The invention also provides the nano carbon hybrid aerogel prepared by the preparation method in the technical scheme. In the invention, the nano carbon hybrid aerogel has the advantages of high electrical conductivity, high specific surface area and large size.
The invention also provides the application of the nano carbon hybrid aerogel in the technical scheme in the field of electrocatalysis. In the present invention, the application preferably includes: in the aspect of electrochemical energy storage, the electrode is used as an electrode of a high-conductivity energy storage device; in the aspect of catalytic characteristics, the material can be directly used as a catalyst, can be used as a catalyst carrier through functionalization or loading of functional nanoparticles, and can effectively improve the catalytic action; meanwhile, the heat insulation and preservation system is also used for a high-end heat insulation and preservation system.
The following will explain the nanocarbon hybrid aerogel provided by the present invention, its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under the anhydrous and oxygen-free conditions, 0.02g of metal sodium is mixed with 20mL of anhydrous dimethylacetamide solution containing sodium naphthalene to obtain an electronic solution containing sodium counter ions, and the mass concentration of naphthol in the anhydrous dimethylacetamide solution containing sodium naphthalene is 6.6 mg/mL;
mixing 5mL of an electronic solution (the concentration of sodium ions is 0.043mmol/mL) containing partial sodium counter ions with 0.026G of carbon nanotubes (single-walled carbon nanotubes with the diameter of 0.8-1.3 nm and the Raman G/D ratio of more than 100) to obtain a polyanionic solution of the carbon nanotubes;
mixing 7mL of the rest electronic solution containing sodium counter ions (the concentration of sodium ions is 0.043mmol/mL) with 0.028g of carbonized nitrogen (lamellar structure carbonized nitrogen, the atomic ratio of nitrogen to carbon is more than 1, and the diameter is 50 nanometers) to obtain a carbonized nitrogen polyanion solution;
and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene at room temperature for a crosslinking reaction for 24 hours to obtain the nano carbon mixed aerogel, wherein the molar ratio of the sum of sodium ions in the carbon nano tube polyanion solution and the nitrogen carbide polyanion solution to the diiodobenzene is 1: 1.
SEM analysis of the nanocarbon hybrid aerogel obtained in this example showed that the nanocarbon hybrid aerogel obtained in this example was used as a catalyst carrier in a direct methanol fuel cell to obtain a catalyst, and SEM analysis of the catalyst showed that the average particle size and size distribution of the nano platinum catalyst are shown in fig. 1(b), and fig. 1(c) shows that the noble metal catalyst is distributed more uniformly, as can be seen from fig. 1.
Fig. 2 is a comparison between the overvoltage interval of the oxygen reduction reaction of the platinum catalyst in the nitrogen carbide, reduced graphene oxide and nanocarbon mixed aerogel carrier and the performance (current density) of the platinum/carbon catalyst carrier in commercial use, and it can be seen from fig. 2 that the nanocarbon mixed aerogel prepared by the invention can greatly improve the current density and the electrocatalytic activity and reduce the dosage of the noble metal catalyst.
Fig. 3 is an optical photograph of the nanocarbon hybrid aerogel prepared in the present example; fig. 4 is a high resolution SEM spectrogram of the nanocarbon hybrid aerogel prepared in this embodiment, and as can be seen from fig. 4, carbon nanotubes and nitrogen carbide in the nanocarbon hybrid aerogel are uniformly distributed and cross-linked to form an integral structure.
Fig. 5 is a curve of void distribution versus specific surface area of the nanocarbon hybrid aerogel prepared in this example, and it can be seen from fig. 5 that the nanocarbon hybrid aerogel fully maintains the characteristic of large surface area of nanocarbon material, and has high specific surface area and nano-scale voids therebetween.
Fig. 6 shows the conductivity and raman spectrum defect analysis of the nanocarbon hybrid aerogel prepared in this example, and as can be seen from fig. 6, the nanocarbon hybrid aerogel prepared in this example has high conductivity and few defects.
Fig. 7 is a measured energy storage characteristic curve of the nanocarbon hybrid aerogel prepared in this embodiment when used in an energy storage device, and as can be seen from fig. 7, the nanocarbon hybrid aerogel prepared in this embodiment as an electrode material of an energy storage capacitor has a specific capacitance up to 333F/g in a TBAP/acetonitrile organic electrolyte.
Example 2
Under the anhydrous and oxygen-free conditions, 0.06g of metal sodium is mixed with anhydrous dimethylacetamide solution containing sodium naphthalene to obtain sodium-containing counter ion electronic solution, and the mass concentration of naphthol in the anhydrous dimethylacetamide solution containing sodium naphthalene is 6.6 mg/mL;
mixing 23mL of electronic solution (the concentration of sodium ions is 0.043mmol/mL) containing partial sodium counter ions with 0.048G of carbon nanotubes (single-walled carbon nanotubes, the diameter of the carbon nanotubes is 0.8' 1.3nm, and the Raman G/D ratio is more than 100) to obtain polyanionic solution of the carbon nanotubes;
mixing 23mL of the rest electronic solution containing sodium counter ions (the concentration of sodium ions is 0.043mmol/mL) with 0.066g of nitrogen carbide (lamellar structure nitrogen carbide, the ratio of nitrogen to carbon atoms is more than 1, and the diameter is 50 nanometers) to obtain a nitrogen carbide polyanion solution;
and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene at room temperature for crosslinking reaction for 15min to obtain the nano carbon mixed aerogel, wherein the molar ratio of the sum of sodium ions in the carbon nano tube polyanion solution and the nitrogen carbide polyanion solution to the diiodobenzene is 1: 1.
Example 3
Under the anhydrous and oxygen-free conditions, 0.02g of metal sodium is mixed with anhydrous dimethylacetamide solution containing sodium naphthalene to obtain sodium-containing counter ion electronic solution, and the mass concentration of naphthol in the anhydrous dimethylacetamide solution containing sodium naphthalene is 6.6 mg/mL;
mixing 4mL of electronic solution (the concentration of sodium ions is 0.043mmol/mL) containing partial sodium counter ions with 0.2G of carbon nanotubes (single-walled carbon nanotubes with the diameter of 0.8-1.3 nm and the Raman G/D ratio of more than 100) to obtain polyanionic solution of the carbon nanotubes;
mixing 4mL of the rest electronic solution containing sodium counter ions (the concentration of sodium ions is 0.043mmol/mL) with 0.018g of carbonized nitrogen (lamellar structure carbonized nitrogen, the atomic ratio of nitrogen to carbon is more than 1, and the diameter is 50 nanometers) to obtain a carbonized nitrogen polyanion solution;
and mixing the carbon nano tube polyanion solution, the nitrogen carbide polyanion solution and the diiodobenzene at room temperature for crosslinking reaction for 15min to obtain the nano carbon mixed aerogel, wherein the molar ratio of the sum of sodium ions in the carbon nano tube polyanion solution and the nitrogen carbide polyanion solution to the diiodobenzene is 1: 1.
The aerogel product manufactured by the embodiment has the heat preservation and insulation characteristics.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
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