CN112645293A - Preparation method of narrow-band-gap carbon nitride material, product and application thereof - Google Patents
Preparation method of narrow-band-gap carbon nitride material, product and application thereof Download PDFInfo
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- CN112645293A CN112645293A CN202011518051.5A CN202011518051A CN112645293A CN 112645293 A CN112645293 A CN 112645293A CN 202011518051 A CN202011518051 A CN 202011518051A CN 112645293 A CN112645293 A CN 112645293A
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Abstract
The invention relates to a preparation method of a narrow-band-gap carbon nitride material, and 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 comprises the steps of taking citric acid and urea as reactants, carrying out hydrothermal reaction on the reactants at the temperature of 150-250 ℃ in the preparation process to obtain a precursor, fully curing the precursor at the temperature of 4-100 ℃, and finally carrying out freeze drying to obtain the narrow-band-gap carbon nitride material.
Description
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-bandgap carbon nitride material, and a product and application thereof.
Background
Graphite phase carbon nitride ((g-C)3N4) The conjugated polymer is a pi conjugated polymer with a two-dimensional layered structure, and is a carbon-nitrogen polymer formed by using a heptazine ring or a triazine ring as a basic structural unit. Carbon nitride has been widely used in the technical fields of photocatalysis, supercapacitors, solar cells, lithium ion or sodium ion batteries, fuel cells and the like in recent years due to its unique advantageous characteristics of two-dimensional nanostructure, semiconductor characteristics, low price, environmental protection, excellent physical and chemical stability, easy synthesis and modification and the like. Carbon nitride materials are now found to have the following properties: photocatalytic properties (photocatalytic decomposition of water and other organic pollutants as a photocatalyst), strong adsorption and reduction of oxygen on the surface (fuel cell), energy storage properties (supercapacitor), two-dimensional layered structure (lithium ion or sodium ion battery), and the like.
The method for preparing the carbon nitride material at present 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 (at a temperature of over 400 ℃) to obtain the carbon nitride material. The common carbon nitride material prepared by the conventional method is generally yellow or orange, has a wide band gap value of about 2.7eV, and can only absorb light with the wavelength less than 450nm in the solar spectrum, but has weak absorption on visible light with a high proportion in the solar spectrum, so that the common carbon nitride material hardly has photoelectric conversion capability, and the application of the common carbon nitride material in the photoelectric related technical field is greatly limited. In addition, carbon nitride is bridged by amino group in amorphous state, and hydrogen bond is formed between hydrogen on the amino group and nitrogen atom on the heptazine ring to construct a two-dimensional nano structure, so that disordered and 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. The carbon nitride material (or other materials) has not been found in the prior art to store solar energy in the material through photoelectric conversion and release the solar energy in the form of electric energy, namely, the carbon nitride material has the characteristics of both photoelectric conversion and charge storage in one material.
Therefore, in order to obtain a carbon nitride material having both photoelectric conversion and charge storage effects and to widen the application range thereof, it is necessary to further research to reduce the band gap of the carbon nitride material, to improve the absorption capability of the carbon nitride material for visible light, and to 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 material is improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a carbon nitride material with narrow band gap; it is a second object of the present invention to provide a carbon nitride material with a narrow band gap; the invention also aims to provide an application of the carbon nitride material with the narrow band gap in the preparation of the light charging electrode.
In order to achieve the purpose, the invention provides the following technical scheme:
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) preserving the hydrothermal reaction product at the temperature of 4-100 ℃ for 10 days-24 months to generate a dark blue solution;
(3) and (3) carrying out freeze drying treatment on the deep blue solution obtained in the step (2) to obtain the narrow-band-gap carbon nitride material.
Preferably, the mass ratio of citric acid to urea in the reaction system in the step (1) is 1: 1-2: 1.
Preferably, the concentration of the mass (total mass of citric acid and 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 for 24-96 h at the temperature of-20 to-90 ℃.
2. The narrow-bandgap carbon nitride material prepared by the above preparation method.
Preferably, the material can absorb visible light with the wavelength of 450-750 nm and ultraviolet light with the wavelength of less than 400 nm.
Preferably, the maximum molar absorptivity ε of the material at 638nm638nm＝130.71L mol-1cm-1；
The material is blue powder, and the microscopic morphology of the material is porous spherical particles formed by a two-dimensional network.
3. The carbon nitride material with narrow band gap is applied to the preparation of the light charging electrode.
Preferably, the method for preparing the light charging electrode specifically comprises the following steps: and adding water into the narrow-bandgap carbon nitride material to prepare slurry, and coating the slurry on FTO conductive glass sintered with a titanium dioxide layer by using a blade coating or spin coating method to obtain the narrow-bandgap carbon nitride light charging electrode.
Preferably, the mass ratio of the narrow-band-gap carbon nitride material to water in the slurry is 1: 0.00001-0.1; the coating thickness of the slurry 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 comprises the steps of taking citric acid and urea as reactants, carrying out hydrothermal reaction on the reactants at the temperature of 150-250 ℃ in the preparation process to obtain a precursor, fully curing the precursor at the temperature of 4-100 ℃, and finally carrying out 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.
2. The invention also discloses a prepared narrow-bandgap carbon nitride material, which has the following basic structural characteristics: 1) triazine ring or heptazine ring is taken as a basic structural unit, and a plurality of graphite domains are contained in the microstructure; 2) the microscopic 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 uniform film material with good ductility in a high-concentration state; 4) the photoelectric conversion performance is remarkable; 5) having a light induced pseudocapacitance characteristics characteristic; 6) the assembled unit cells can store light energy and release it in the form of electrical energy.
3. The band gap of the prepared carbon nitride material with the narrow band gap is reduced to about 1.7eV from the existing 2.7eV, the carbon nitride material can absorb visible light with the wavelength of 450-750 nm and ultraviolet light with the wavelength of less than 400nm, and the carbon nitride material has strong absorption on the visible light with the wavelength of 500-700 nm; has an absorption peak at 638nm and a maximum molar absorptivity epsilon638nmUp to 130.71L mol- 1cm-1. The material has remarkable photoelectric conversion performance and photoinduction pseudocapacitance characteristics characteristics, and has good application effect in the aspect of preparing a light 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 objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with 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 diagram showing the UV-VIS absorption spectrum (a) and the UV-VIS transmission spectrum (b) of a carbon nitride material (PCN) with a narrow band gap prepared according to the present invention;
FIG. 4 is a schematic of the layered structure of an electrode made using the narrow bandgap carbon nitride material (PCN) made by the present invention;
fig. 5 shows cyclic voltammetry curves (a) and constant current charge-discharge curves (b) of a narrow bandgap carbon nitride photo-charged electrode.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
The preparation method of the narrow-band-gap carbon nitride material comprises the following specific steps:
(1) mixing 29.25g of citric acid and 15.00g of urea and dissolving 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 3h to obtain a hydrothermal reaction product;
(3) storing the hydrothermal reaction product at 25 ℃ for 2 months to generate a dark blue solution;
(4) and (4) carrying out freeze drying (drying at the temperature of minus 80 ℃ for 48h) on the dark blue solution obtained in the step (3) to obtain blue powder, namely the narrow-band-gap carbon nitride material.
Example 2
The preparation method of 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 6h to obtain a hydrothermal reaction product;
(3) storing the hydrothermal reaction product at 4 ℃ for 24 months to generate a dark blue solution;
(4) and (4) carrying out freeze drying (drying at the temperature of minus 20 ℃ for 96h) treatment 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 of the narrow-band-gap carbon nitride material comprises the following specific steps:
(1) mixing and dissolving 100.0g of citric acid and 50.0g of urea 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) storing the hydrothermal reaction product at 100 ℃ for 10 days to generate a dark blue solution;
(4) and (4) carrying out freeze drying (drying at the temperature of minus 90 ℃ for 24h) treatment 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 carbon nitride material with narrow band gap prepared in example 1 is shown in fig. 1, the TEM thereof is shown in fig. 2, and the schematic diagram of the microstructure thereof is as follows:
the microscopic morphology of the narrow-band-gap 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 thin film material with good ductility and uniformity can be formed in a high-concentration state, and a thin film with good adhesiveness and uniformity can be formed on the surfaces of materials such as conductive glass, metal oxide and metal without high-temperature calcination.
The prepared carbon nitride material (PCN) with narrow band gap is subjected to ultraviolet-visible absorption spectrum and ultraviolet-visible transmission spectrum tests, and the test results are shown in fig. 3, wherein a is an ultraviolet-visible absorption spectrum chart, and b is an ultraviolet-visible transmission spectrum chart. As can be seen from a in FIG. 3, the carbon nitride material (PCN) with narrow band gap prepared by the invention can absorb visible light with the wavelength of 450-750 nm and light with the wavelength of less than 400nmUltraviolet light, wherein the ultraviolet light has strong absorption effect on visible light with the wavelength of 500-700 nm, and has an absorption peak at 638 nm; as can be seen from b in FIG. 3, the carbon nitride material (PCN) with narrow band gap prepared by the present invention has the maximum molar absorptivity ε when excited at 638nm638nm＝130.71L mol-1cm-1And the band gap of the material is reduced to 1.7 eV.
Similarly, the carbon nitride materials with narrow band gap prepared in examples 2 and 3 also have the properties shown in the material in example 1, which shows that the carbon nitride material with narrow band gap can be obtained by the preparation method of the invention, and the basic structural characteristics are as follows: 1) triazine ring or heptazine ring is taken as a basic structural unit, and a plurality of graphite domains are contained in the microstructure; 2) the microscopic 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 uniform film material with good ductility in a high-concentration state; 4) the photoelectric conversion performance is remarkable; 5) having a light induced pseudocapacitance characteristics characteristic; 6) the assembled unit cells can store light energy and release it in the form of electrical energy. Meanwhile, the band gap of the prepared carbon nitride material with the narrow band gap is reduced to about 1.7eV from the existing 2.7eV, the carbon nitride 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 absorptivity epsilon638nmUp to 130.71L mol-1cm-1. The material has remarkable photoelectric conversion performance and pseudocapacitance characteristics characteristic, and has good application effect in the aspect of preparing a light charging electrode.
2. The narrow-bandgap carbon nitride material (PCN) prepared in example 1 is added into water according to a mass ratio of 1:0.01 (the mass ratio can be adjusted between 1:0.00001 and 0.1) to prepare a slurry, and the slurry is coated on FTO conductive glass with a sintered titanium dioxide layer in a thickness of 100 μm (the coating thickness can be adjusted between 0.01 and 1000 μm) by a blade coating or spin coating method, so as to obtain the narrow-bandgap carbon nitride photo-charging electrode, wherein a schematic diagram of a 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.
The prepared narrow-bandgap carbon nitride light charging electrode is subjected to cyclic voltammetry characteristics and constant current charge and discharge tests to obtain a cyclic voltammetry characteristic curve as shown in a in fig. 5, and a constant current charge and discharge curve as shown in b in fig. 5. Under the condition of illumination, 50mV s is used for the prepared narrow-bandgap carbon nitride photo-charging electrode-1The cyclic voltammogram test was performed at a scan rate of 695mV, where the oxidation current peak at 695mV was from
The peak of the reduction current at 500mV is from
As can be seen from the CV curve of a in fig. 5, the uncharged electrode prepared from the narrow bandgap carbon nitride material of the present invention exhibits significant pseudocapacitance characteristics; and in the dark state this pair of redox current peaks does not appear, further suggesting that the pseudocapacitive behavior exhibited by narrow bandgap carbon nitride is indeed due to illumination. At 0.4mA cm-2The prepared carbon nitride optical charging electrode with narrow band gap is tested under the conditions of illumination and dark state constant current charging and discharging performance, and as can be seen from the constant current charging and discharging curve b in figure 5, the constant current charging and discharging performance is 100mW cm-2Under illumination, the narrow-band-gap carbon nitride optical charging electrode generates effective charge and discharge, and 5.2mF cm is obtained-2Area specific capacitance of (d); in the dark state, the density is only 1.58mF cm-2Area to capacitance.
Similarly, the same conclusion can be obtained by subjecting the narrow bandgap carbon nitride materials prepared in examples 2 and 3 to the same test as described above. Therefore, the light charging electrode prepared from the narrow-band-gap carbon nitride material has remarkable photoelectric conversion performance and pseudocapacitance characteristics characteristics, and a single battery formed by assembling the light charging electrode can store light energy and release the light energy in the form of electric energy, so that the total energy conversion efficiency of not less than 0.6% is obtained.
In summary, the invention discloses a preparation method of a carbon nitride material with narrow band gap, which adopts citric acid and urea as reactants and reacts firstly in the preparation processCarrying out hydrothermal reaction on the materials at the temperature of 150-250 ℃ to obtain a precursor, fully curing the precursor at the temperature of 4-100 ℃, and finally carrying out 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-bandgap carbon nitride material prepared by the method, and the material has the following basic structural characteristics: 1) triazine ring or heptazine ring is taken as a basic structural unit, and a plurality of graphite domains are contained in the microstructure; 2) the microscopic 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 uniform film material with good ductility in a high-concentration state; 4) the photoelectric conversion performance is remarkable; 5) having a light induced pseudocapacitance characteristics characteristic; 6) the assembled unit cells can store light energy and release it in the form of electrical energy. In addition, the band gap of the prepared carbon nitride material with the narrow band gap is reduced to about 1.7eV from the existing 2.7eV, the carbon nitride 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 absorptivity epsilon638nmUp to 130.71L mol-1cm-1. The material has remarkable photoelectric conversion performance and pseudocapacitance characteristics characteristic, and has good application effect in the aspect of preparing a light charging electrode.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing a narrow bandgap carbon nitride material, 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) preserving the hydrothermal reaction product at the temperature of 4-100 ℃ for 10 days-24 months to generate a dark blue solution;
(3) and (3) carrying out 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 the citric acid to the 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 freeze-drying in step (3) is carried out under the following conditions: drying for 24-96 h at the temperature of-20 to-90 ℃.
5. A narrow bandgap carbon nitride material produced by the production method according to any one of claims 1 to 4.
6. The narrow bandgap carbon nitride material according to claim 5, wherein said material is capable of absorbing visible light with a wavelength of 450 to 750nm and ultraviolet light with a wavelength of less than 400 nm.
7. The narrow bandgap carbon nitride material of claim 5, wherein the material has a maximum molar absorptivity ε at 638nm638nm＝130.71L mol-1cm-1；
The material is blue powder, and the microscopic morphology of the material is porous spherical particles formed by a two-dimensional network.
8. Use of the narrow bandgap carbon nitride material of any one of claims 5 to 7 in the preparation of a photo-charged electrode.
9. The use according to claim 8, wherein the method of preparing a photo-charged electrode is in particular: and adding water into the narrow-bandgap carbon nitride material to prepare slurry, and coating the slurry on FTO conductive glass sintered with a titanium dioxide layer by using a blade coating or spin coating method to obtain the narrow-bandgap carbon nitride light charging electrode.
10. The use according to claim 8, wherein the mass ratio of the narrow bandgap carbon nitride material to water in the slurry is 1:0.00001 to 0.1; the coating thickness of the slurry in the coating process is 0.01-1000 mu m.
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