CN112645293B - Preparation method of narrow-band-gap carbon nitride material, and product and application thereof - Google Patents

Preparation method of narrow-band-gap carbon nitride material, and product and application thereof Download PDF

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CN112645293B
CN112645293B CN202011518051.5A CN202011518051A CN112645293B CN 112645293 B CN112645293 B CN 112645293B CN 202011518051 A CN202011518051 A CN 202011518051A CN 112645293 B CN112645293 B CN 112645293B
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carbon nitride
nitride material
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唐笑
何利蓉
张灵
李艳虹
相国涛
周贤菊
谢广新
凌发令
姚璐
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Chongqing University of Post and Telecommunications
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Abstract

The invention relates to a preparation method of a narrow-band-gap carbon nitride material, a product and application thereof, and belongs to the technical field of solar photoelectric conversion and storage. The invention discloses a preparation method of a narrow band gap carbon nitride material, which is characterized in that citric acid and urea are used as reactants, the reactants are subjected to hydrothermal reaction at the temperature of 150-250 ℃ to obtain a precursor in the preparation process, the precursor is fully cured at the temperature of 4-100 ℃ and finally subjected to freeze drying, so that the narrow band gap carbon nitride material is obtained, has obvious photoelectric conversion performance and photoinduction pseudocapacitance characteristics, and has good application effect in the aspect of preparing a photo-charging electrode.

Description

Preparation method of narrow-band-gap carbon nitride material, and product and application thereof
Technical Field
The invention belongs to the technical field of solar photoelectric conversion and storage, and particularly relates to a preparation method of a narrow-band-gap carbon nitride material, a product and application thereof.
Background
Graphite phase carbon nitride ((g-C) 3 N 4 ) Is a pi conjugated polymer with a two-dimensional lamellar structure, and is a carbon-nitrogen polymer formed by taking a heptyl ring or a triazine ring as a basic structural unit. Carbon nitride is low-cost, environment-friendly and excellent due to its two-dimensional nano structure, semiconductor characteristicsThe polymer is widely applied in the technical fields of photocatalysis, super capacitors, solar cells, lithium ion or sodium ion batteries, fuel cells and the like in recent years. Currently, carbon nitride materials are found to have characteristics of: photocatalytic properties (as a photocatalyst for photocatalytic decomposition of water and other organic pollutants), strong adsorption and reduction of oxygen on the surface (fuel cells), energy storage properties (supercapacitors), a two-dimensional layered structure (lithium ion or sodium ion cells), and the like.
The current method for preparing the carbon nitride material mainly comprises the steps of carrying out hydrothermal reaction on reactants containing nitrogen and carbon to obtain a precursor, and then carrying out heat treatment (more than 400 ℃) to obtain the carbon nitride material. The common carbon nitride material prepared by the conventional method is generally yellow or orange, has a wider band gap value of about 2.7eV, can only absorb light with the wavelength smaller than 450nm in the solar spectrum, and has weaker absorption to visible light with very high proportion in the solar spectrum, so that the common carbon nitride material has almost no photoelectric conversion capability, and is greatly limited in application in the related technical field of photoelectricity. In addition, carbon nitride is bridged by amino groups in an amorphous state, and a two-dimensional nano structure is constructed by forming hydrogen bonds between hydrogen on the amino groups and nitrogen atoms on the heptazine ring, so that irregular microscopic morphology is usually caused when polycondensation or crystallization is carried out at high temperature, the performance of the carbon nitride on free charge storage is seriously influenced, and the application of the carbon nitride in the aspect of energy storage technology is greatly reduced. Carbon nitride materials (or other materials) have not been found in the prior art to store solar energy in the material by photoelectric conversion and release it as electrical energy, i.e. to have both photoelectric conversion and charge storage effects in one material.
Therefore, in order to obtain a carbon nitride material with both photoelectric conversion and charge storage effects and to widen the application range thereof, further research is necessary, which can reduce the band gap of the carbon nitride material, improve the absorption capacity of the carbon nitride material to visible light, and improve the photoelectric conversion performance of the carbon nitride material; meanwhile, the ordered porous material constructed by the two-dimensional nano structure can be obtained, and the charge storage performance of the porous material is improved.
Disclosure of Invention
Accordingly, one of the objectives of the present invention is to provide a method for preparing a narrow bandgap carbon nitride material; the second object of the present invention is to provide a narrow bandgap carbon nitride material; the invention further aims to provide an application of the narrow-bandgap carbon nitride material in preparation of a photo-charging electrode.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a method for preparing a narrow bandgap carbon nitride material, the method comprising the steps of:
(1) Carrying out hydrothermal reaction on a reaction system containing citric acid and urea at the temperature of 150-250 ℃ for 0.5-6 h to obtain a hydrothermal reaction product;
(2) The hydrothermal reaction product is preserved for 10 days to 24 months at the temperature of 4 to 100 ℃ to generate a deep blue solution;
(3) And (3) performing freeze drying treatment on the deep blue solution obtained in the step (2) to obtain the narrow band gap carbon nitride material.
Preferably, in the reaction system in the step (1), the mass ratio of the citric acid to the urea is 1:1-2:1.
Preferably, the concentration of the mass (the total mass of the citric acid and the urea) of the reaction system in the step (1) is 5-150 g/L, and the solvent in the reaction system is water.
Preferably, the specific conditions of the freeze-drying in the step (3) are as follows: drying at-20 to-90 deg.c for 24-96 hr.
2. The narrow band gap carbon nitride material prepared by the preparation method.
Preferably, the material is capable of absorbing visible light having a wavelength of 450 to 750nm and ultraviolet light having a wavelength of less than 400 nm.
Preferably, the material has a maximum molar absorption coefficient ε at 638nm 638nm ＝130.71L mol -1 cm -1 ；
The material is blue powder, and the microscopic morphology of the material is a two-dimensional network to form porous spherical particles.
3. The narrow band gap carbon nitride material is applied to the preparation of the photo-charging electrode.
Preferably, the method for preparing the photo-charging electrode specifically comprises the following steps: and adding water into the narrow-band-gap carbon nitride material to prepare slurry, and coating the slurry on the FTO conductive glass sintered with the titanium dioxide layer by a blade coating or spin coating method to obtain the narrow-band-gap carbon nitride photo-charging electrode.
Preferably, the mass ratio of the narrow-bandgap carbon nitride material to the water in the slurry is 1:0.00001-0.1; the thickness of the slurry applied in the coating process is 0.01-1000 mu m.
The invention has the beneficial effects that:
1. the invention discloses a preparation method of a narrow band gap carbon nitride material, which is characterized in that citric acid and urea are used as reactants, the reactants are subjected to hydrothermal reaction at the temperature of 150-250 ℃ to obtain a precursor in the preparation process, the precursor is fully cured at the temperature of 4-100 ℃, and finally freeze drying is carried out to obtain the narrow band gap carbon nitride material. The preparation method is simple and easy to operate, and is easy for industrial mass preparation of the narrow band gap carbon nitride material.
2. The invention also discloses the prepared narrow band gap carbon nitride material, which has the following basic structural characteristics: 1) Taking triazine ring or heptazine ring as a basic structural unit, and containing a large number of graphite domains in a microstructure; 2) The microcosmic morphology is a three-dimensional porous sphere constructed by a two-dimensional nano structure, and the apparent morphology is blue powder; 3) Is easy to dissolve in water, and can form a film material with good ductility and uniformity in a high concentration state; 4) The photoelectric conversion performance is remarkable; 5) Has the light-induced capacitance characteristic; 6) The assembled battery cells may store light energy and release it as electrical energy.
3. The band gap of the narrow band gap carbon nitride material prepared by the invention is reduced to about 1.7eV from the existing 2.7eV, and the narrow band gap carbon nitride material can absorb visible light with the wavelength of 450-750 nm and ultraviolet light with the wavelength of less than 400nm, wherein the narrow band gap carbon nitride material has strong absorption to the visible light with the wavelength of 500-700 nm; has an absorption peak at 638nm and a maximum molar absorption coefficient epsilon 638nm Can reach 130.71L mol - 1 cm -1 . The material has obvious photoelectric conversion performance and photoinduced performanceThe lead has good capacitance characteristic and good application effect in the aspect of preparing the photo-charging electrode.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a narrow bandgap carbon nitride material prepared in example 1;
FIG. 2 is a TEM image of the narrow bandgap carbon nitride material prepared in example 1;
FIG. 3 is a graph of ultraviolet-visible absorption spectrum (a) and a graph of ultraviolet-visible transmission spectrum (b) of a narrow bandgap carbon nitride material (PCN) prepared according to the present invention;
FIG. 4 is a schematic view of a layered structure of an electrode made of a narrow bandgap carbon nitride material (PCN) made in accordance with the present invention;
fig. 5 shows cyclic voltammetry characteristic (a) and constant current charge-discharge (b) curves of a narrow bandgap carbon nitride photo-charging electrode.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
The preparation method for preparing the narrow band gap carbon nitride material comprises the following specific steps:
(1) 29.25g of citric acid and 15.00g of urea are mixed and dissolved in 1L of water to form a reaction system with the concentration of 44.25 g/L;
(2) Carrying out hydrothermal reaction on the reaction system at the temperature of 200 ℃ for 3 hours to obtain a hydrothermal reaction product;
(3) Preserving the hydrothermal reaction product at 25 ℃ for 2 months to generate a deep blue solution;
(4) And (3) performing freeze drying (drying at the temperature of-80 ℃ for 48 hours) on the deep blue solution obtained in the step (3) to obtain blue powder, namely the narrow band gap carbon nitride material.
Example 2
The preparation method for preparing the narrow band gap carbon nitride material comprises the following specific steps:
(1) 2.5g of citric acid and 2.5g of urea are mixed and dissolved in 1L of water to form a reaction system with the concentration of 5.0 g/L;
(2) Carrying out hydrothermal reaction on the reaction system at the temperature of 150 ℃ for 6 hours to obtain a hydrothermal reaction product;
(3) Preserving the hydrothermal reaction product at the temperature of 4 ℃ for 24 months to generate a deep blue solution;
(4) And (3) performing freeze drying (drying at the temperature of minus 20 ℃ for 96 hours) on the deep blue solution obtained in the step (3) to obtain the blue powder narrow band gap carbon nitride material.
Example 3
The preparation method for preparing the narrow band gap carbon nitride material comprises the following specific steps:
(1) 100.0g of citric acid and 50.0g of urea are mixed and dissolved in 1L of water to form a reaction system with the concentration of 150 g/L;
(2) Carrying out hydrothermal reaction on the reaction system at the temperature of 250 ℃ for 0.5h to obtain a hydrothermal reaction product;
(3) Preserving the hydrothermal reaction product at 100 ℃ for 10 days to generate a deep blue solution;
(4) And (3) performing freeze drying (drying at the temperature of minus 90 ℃ for 24 hours) on the deep blue solution obtained in the step (3) to obtain the blue powder narrow band gap carbon nitride material.
Performance testing
1. The narrow bandgap carbon nitride material prepared in example 1 is shown in fig. 1, the TEM is shown in fig. 2, and the microstructure is schematically shown as follows:
Figure BDA0002848630070000041
the microscopic morphology of the narrow-bandgap carbon nitride material (PCN) prepared by the invention is three-dimensional porous spherical particles constructed by a two-dimensional nanostructure, the apparent morphology is blue powder, the material is easy to dissolve in water, a film material with good ductility and uniformity can be formed in a high concentration state, and a film with good adhesiveness and good uniformity can be formed on the surfaces of materials such as conductive glass, metal oxide, metal and the like without high-temperature calcination.
The narrow bandgap carbon nitride material (PCN) prepared above was subjected to ultraviolet-visible absorption spectrum and ultraviolet-visible transmission spectrum tests, the test results are shown in fig. 3, wherein a is an ultraviolet-visible absorption spectrum and b is an ultraviolet-visible transmission spectrum. As can be seen from fig. 3 a, the narrow bandgap carbon nitride material (PCN) prepared by the present invention can absorb visible light with a wavelength of 450-750 nm and ultraviolet light with a wavelength of less than 400nm, wherein the material has a strong absorption effect on visible light with a wavelength of 500-700 nm, and has an absorption peak at 638 nm; as can be seen from FIG. 3 b, the narrow bandgap carbon nitride material (PCN) prepared according to the present invention is excited at 638nm and has a maximum molar absorption coefficient ε 638nm ＝130.71L mol -1 cm -1 And the band gap of the material is reduced to 1.7eV.
Likewise, the narrow bandgap carbon nitride materials prepared in example 2 and example 3 also have properties similar to those shown in example 1, indicating that narrow bandgap carbon nitride materials can be obtained by the preparation method of the present invention, the basic structural characteristics of which are: 1) Taking triazine ring or heptazine ring as a basic structural unit, and containing a large number of graphite domains in a microstructure; 2) The microcosmic morphology is a three-dimensional porous sphere constructed by a two-dimensional nano structure, and the apparent morphology is blue powder; 3) Is easy to dissolve in water and can form a high and uniform ductility in a high concentration stateA film material; 4) The photoelectric conversion performance is remarkable; 5) Has the light-induced capacitance characteristic; 6) The assembled battery cells may store light energy and release it as electrical energy. Meanwhile, the band gap of the prepared narrow band gap carbon nitride material is reduced to about 1.7eV from the existing 2.7eV, and the material can absorb visible light with the wavelength of 450-750 nm and ultraviolet light with the wavelength of less than 400nm, and has strong absorption on the visible light with the wavelength of 500-700 nm; has an absorption peak at 638nm and a maximum molar absorption coefficient epsilon 638nm Can reach 130.71L mol -1 cm -1 . The material has obvious photoelectric conversion performance and capacitance characteristic, and has good application effect in the aspect of preparing the photo-charging electrode.
2. The narrow bandgap carbon nitride material (PCN) prepared in example 1 was added to water to prepare a slurry according to a mass ratio of 1:0.01 (the mass ratio can be adjusted between 1:0.00001 and 0.1), and the slurry was coated on FTO conductive glass sintered with a titanium dioxide layer by a doctor blade or spin coating method to a thickness of 100 μm (the coating thickness can be adjusted between 0.01 and 1000 μm), so as to obtain a narrow bandgap carbon nitride photo-charging electrode, and a schematic diagram of the layered structure of the electrode is shown in fig. 4, which illustrates that the narrow bandgap carbon nitride photo-charging electrode is composed of three layers of carbon nitride material/titanium dioxide/FTO conductive glass.
And (3) carrying out cyclic volt-ampere characteristic and constant current charge-discharge test on the prepared narrow band gap carbon nitride photo-charge electrode, wherein the obtained cyclic volt-ampere characteristic curve is shown as a in figure 5, and the constant current charge-discharge curve is shown as b in figure 5. Charging the prepared narrow band gap carbon nitride photo-charge electrode with 50mV s under illumination condition -1 Is tested by cyclic voltammogram, wherein the oxidation current peak at 695mV is from
Figure BDA0002848630070000061
The reduction current peak at 500mV comes from +.>
Figure BDA0002848630070000062
As can be seen from the CV curve of fig. 5 a, the photo-charged electrode prepared from the narrow bandgap carbon nitride material of the invention exhibits significant pseudocapacitance characteristics; and in the dark stateIn the case where the pair of redox current peaks does not appear, this further illustrates that the pseudocapacitive behavior exhibited by the narrow bandgap carbon nitride is indeed caused by illumination. At 0.4mA cm -2 The constant current charge and discharge performance of the narrow band gap carbon nitride photo-charge electrode prepared above under the illumination and dark state was tested under constant current density, and as can be seen from the constant current charge and discharge curve of FIG. 5 b, the charge and discharge performance was measured under 100mW cm -2 Under illumination, the narrow band gap carbon nitride photo-charging electrode generates effective charge and discharge to obtain 5.2mF cm -2 Area ratio capacitance of (2); in the dark state, only 1.58mF cm -2 Area ratio capacitance of (2).
Similarly, the narrow bandgap carbon nitride materials prepared in example 2 and example 3 above were subjected to the same test as described above, and the same conclusion was reached. Therefore, the photo-charging electrode prepared from the narrow band gap carbon nitride material has remarkable photoelectric conversion performance and capacitance characteristic, and the single battery assembled by the photo-charging electrode can store light energy and release the light energy in the form of electric energy, so that the total energy conversion efficiency is not lower than 0.6%.
In summary, the invention discloses a preparation method of a narrow band gap carbon nitride material, which comprises the steps of taking citric acid and urea as reactants, carrying out hydrothermal reaction on the reactants at the temperature of 150-250 ℃ to obtain a precursor in the preparation process, fully curing the precursor at the temperature of 4-100 ℃, and finally freeze-drying to obtain the narrow band gap carbon nitride material. The preparation method is simple and easy to operate, and is easy for industrial mass preparation of the narrow band gap carbon nitride material. The invention also discloses a narrow band gap carbon nitride material prepared by the method, which has the following basic structural characteristics: 1) Taking triazine ring or heptazine ring as a basic structural unit, and containing a large number of graphite domains in a microstructure; 2) The microcosmic morphology is a three-dimensional porous sphere constructed by a two-dimensional nano structure, and the apparent morphology is blue powder; 3) Is easy to dissolve in water, and can form a film material with good ductility and uniformity in a high concentration state; 4) The photoelectric conversion performance is remarkable; 5) Has the light-induced capacitance characteristic; 6) The assembled battery cells may store light energy and release it as electrical energy. In addition, the narrow band gap carbon nitride prepared by the inventionThe band gap of the material is reduced to about 1.7eV from the existing 2.7eV, and the material can absorb visible light with the wavelength of 450-750 nm and ultraviolet light with the wavelength of less than 400nm, and has strong absorption to the visible light with the wavelength of 500-700 nm; has an absorption peak at 638nm and a maximum molar absorption coefficient epsilon 638nm Can reach 130.71L mol -1 cm -1 . The material has obvious photoelectric conversion performance and capacitance characteristic, and has good application effect in the aspect of preparing the photo-charging electrode.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.

Claims (10)

1. The preparation method of the narrow band gap carbon nitride material is characterized by comprising the following steps of:
(1) Carrying out hydrothermal reaction on a reaction system containing citric acid and urea at the temperature of 150-250 ℃ for 0.5-6 h to obtain a hydrothermal reaction product;
(2) The hydrothermal reaction product is preserved for 10 days to 24 months at the temperature of 4 to 100 ℃ to generate a deep blue solution;
(3) And (3) performing freeze drying treatment on the deep blue solution obtained in the step (2) to obtain the narrow band gap carbon nitride material.
2. The preparation method according to claim 1, wherein the mass ratio of citric acid to urea in the reaction system in the step (1) is 1:1-2:1.
3. The preparation method according to claim 1, wherein the mass concentration of the reaction system in the step (1) is 5-150 g/L, and the solvent in the reaction system is water.
4. The method according to claim 1, wherein the specific conditions for freeze-drying in step (3) are: drying at-20 to-90 deg.c for 24-96 hr.
5. The narrow bandgap carbon nitride material prepared by the method according to any one of claims 1 to 4, wherein the material has a microstructure of two-dimensional network to form porous spherical particles.
6. The narrow bandgap carbon nitride material according to claim 5, wherein said material is capable of absorbing visible light having a wavelength of 450-750 nm and ultraviolet light having a wavelength of less than 400 nm.
7. The narrow bandgap carbon nitride material according to claim 5, wherein said material has a maximum molar absorption coefficient epsilon at 638nm 638nm ＝130.71L mol -1 cm -1 ；
The material is blue powder.
8. Use of a narrow bandgap carbon nitride material according to any of claims 5 to 7 for the preparation of a photo-charging electrode.
9. The use according to claim 8, wherein the method for preparing the photo-charging electrode is specifically: and adding water into the narrow-band-gap carbon nitride material to prepare slurry, and coating the slurry on the FTO conductive glass sintered with the titanium dioxide layer by a blade coating or spin coating method to obtain the narrow-band-gap carbon nitride photo-charging electrode.
10. The use according to claim 9, wherein the mass ratio of the narrow bandgap carbon nitride material to the water in the slurry is 1:0.00001-0.1; the thickness of the slurry applied in the coating process is 0.01-1000 mu m.
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