CN116099565A - Red supermolecule graphite phase carbon nitride photocatalyst capable of improving visible light utilization rate and preparation method thereof - Google Patents
Red supermolecule graphite phase carbon nitride photocatalyst capable of improving visible light utilization rate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a red supermolecule graphite phase carbon nitride photocatalyst for improving visible light utilization rate and a preparation method thereof. Mixing ethanol and deionized water with cyanuric acid, and stirring. Then, P-MA was added to the cyanuric acid solution, and nitric acid was added. Then placing the mixture into an oil bath pot, stirring the mixture at the temperature of 80 ℃, and then placing the mixture into a vacuum drying oven for drying to obtain a yellow precursor with high viscosity. And finally, placing the precursor into a crucible, placing the crucible into a muffle furnace for calcination to enable the precursor to undergo phase change, and cooling the precursor to room temperature. Thus obtaining ACCN with ultra-high light absorption capacity. Compared with the method for forming supermolecule self-assembly by using melamine and cyanuric acid, the photocatalyst prepared by the method has stronger light absorption capacity to visible light and higher hydrogen evolution performance, and the used raw materials are low in cost, easy to obtain, environment-friendly and capable of being prepared on a large scale.
Description
Technical Field
The invention belongs to the field of photocatalytic functional materials, and relates to a red supermolecule graphite phase carbon nitride photocatalyst capable of improving the utilization rate of visible light and a preparation method thereof.
Background
The future energy crisis is increasingly exacerbated by the excessive use of non-renewable energy sources such as fossil fuels. There is an urgent need for clean, pollution-free renewable energy sources. Since the discovery of oxygen generation by oxidation reaction of water molecules on the surface of a titanium dioxide electrode under ultraviolet irradiation by Japanese scientist vine island in 1967, research on human photocatalytic technology has been well developed, g-C 3 N 4 The preparation is favored by researchers because of the advantages of simple preparation, no environmental pollution, abundant storage of constituent elements, good stability and the like. However, the lower photocatalytic efficiency still limits the further practical application, and the following three main reasons are: first, due to g-C 3 N 4 The nano material has larger surface energy and can be polymerized to form g-C according to the principle that the lower the energy is, the more stable 3 N 4 The agglomeration phenomenon spontaneously occurs to reduce the surface energy, so that the active sites of the photocatalyst cannot be fully exposed; secondly, the general photocatalyst can only absorb and utilize ultraviolet light (less than 400 nm) accounting for 3-5% of solar spectrum, but does not fully utilize visible light (400-700 nm) with abundant content (42-43%); thirdly, because stronger coulomb force exists between the photogenerated electrons and the photogenerated holes, the photogenerated carriers are easy to be compounded, and only a small part of the photogenerated electrons participate in hydrogen evolution reaction. Thus, researchers have sought to overcome the three difficulties mentioned above by various means. The ACCN obtained by the invention has 65.173m 2 A large specific surface area per g and promotes a lone pair of electrons at the nitrogen atom at n.fwdarw.pi * The absorption rate of visible light of 400nm-650nm is obviously improved. Therefore, the ACCN prepared by the method has important significance and reference on the problem of improving the utilization rate of visible light.
In the disclosed supermolecule self-assembly method using cyanuric acid and melamine, the photocatalyst is focused more on the problems of obtaining large specific surface area and reducing the recombination rate of photo-generated carriers through modification of photocatalyst materials, but the problem of widening the absorption of visible light still exists, and the invention ensures that nitrate ions and cyanuric acid cooperatively regulate and control the polymerization of precursor melamine through protonation treatment of the precursor by nitric acid, so that the structure of a heptazine ring unit is distorted, the order degree of ordered melem rings is damaged to a certain extent, and lone pair electrons on nitrogen atoms in the melem rings can also generate n- & pi * Excitation, thereby making moreThe photo-generated carriers participate in hydrogen evolution reaction, the obtained ACCN can absorb wavelengths of about 400nm to 650nm, the light utilization rate of a sample in a visible light region is greatly improved, and the sample has 65m 2 The specific surface area of the catalyst provides a large number of active sites for catalytic reaction, and has important significance in photocatalytic hydrogen evolution academic research.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a red supermolecule graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light and a preparation method thereof, which make up for the g-C in the prior art 3 N 4 The utilization ratio of visible light is insufficient. According to the method, melamine is treated by nitric acid to obtain protonated melamine, the protonated melamine and cyanuric acid form a new supermolecule self-assembled complex, nitric acid is added in the process of forming the complex, and after drying by a vacuum drying oven, a yellow brown precursor with larger viscosity can be obtained, and after phase transition occurs by high-temperature calcination, ACCN with ultrahigh light absorption capacity can be obtained.
Technical proposal
The preparation method of the red supermolecule graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light is characterized by comprising the following steps:
step 1: weighing melamine with the weight of 1-2 g, putting the melamine into concentrated nitric acid with the weight of 25-75 ml, and uniformly stirring;
step 2: filtering melamine treated by nitric acid in the step 1, washing the melamine with deionized water for a plurality of times to obtain a solid product, adding the solid product into cyanuric acid solution, and carrying out ultrasonic treatment;
the cyanuric acid solution is a mixed solution of 20-60 ml of deionized water, 20-60 ml of absolute ethyl alcohol and 1-3 g of cyanuric acid;
step 3: stirring the mixed solution in an oil bath at 70-90 ℃ for 4-12 hours, and then drying to obtain a yellow brown precursor;
step 4: grinding the yellow brown precursor, then placing the ground yellow brown precursor into a crucible, placing the crucible into a muffle furnace, heating to 530-550 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 2-4 h, and cooling to room temperature to obtain light red powder, namely ACCN.
The above ratio is a measure of preparing one part.
The concentration of the concentrated nitric acid is 68%.
The step 1 of stirring uniformly adopts a magnetic stirrer to stir for 1-3 h.
The filter paper is adopted for the filtration in the step 2.
And step 2, washing with deionized water three times.
And step 2, adding the solution into cyanuric acid solution, and performing ultrasonic treatment for 30-60 min.
The mixed solution of cyanuric acid is stirred for at least 30min when mixed.
And the step 3 is to put the materials into a vacuum drying oven to be dried at 75-90 ℃.
The red supermolecule graphite phase carbon nitride photocatalyst prepared by the method is characterized in that: the red supermolecular graphite phase carbon nitride ACCN catalyst has a molecular weight of 65.173m 2 A large specific surface area per g and promotes a lone pair electron at the nitrogen atom at n.fwdarw.pi * The absorption rate of visible light of 400nm-650nm is obviously improved by 2.18 times compared with CCN prepared by the traditional method.
Advantageous effects
The red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light and the preparation method thereof provided by the invention are red supermolecular graphite phase carbon nitride (g-C) for improving the utilization rate of visible light 3 N 4 ) The photocatalyst and the preparation method are used for obtaining red graphite phase carbon nitride (ACCN) with enhanced light absorption capacity through a simple two-step method. Firstly adding melamine into concentrated nitric acid for protonation treatment for one hour, filtering the nitric acid through filter paper, and then washing the solution three times by deionized water to obtain protonated melamine (P-MA). Next, ethanol and deionized water were separately taken in a beaker, cyanuric acid was added to the beaker and stirred for half an hour. Then adding the P-MA into the prepared cyanuric acid solution, and then dripping a proper amount of nitric acid into the solution by using a rubber head dropper. Since the P-MA agglomeration phenomenon is serious, melamine is formed more effectivelyAnd supermolecule self-assembly of cyanuric acid, firstly, treating cyanuric acid solution added with P-MA by using ultrasonic wave, then placing in an oil bath pot, stirring at 80 ℃, and then placing in a vacuum drying oven for drying to obtain yellow precursor with high viscosity. And finally, placing the precursor into a crucible, placing the crucible into a muffle furnace for calcination to enable the precursor to undergo phase change, and cooling the precursor to room temperature. Thus obtaining ACCN with ultra-high light absorption capacity. Compared with the method for forming supermolecule self-assembly by using melamine and cyanuric acid, the photocatalyst prepared by the method has stronger light absorption capacity to visible light and higher hydrogen evolution performance, and the used raw materials are low in cost, easy to obtain, environment-friendly and capable of being prepared on a large scale.
The beneficial effects of the invention are as follows: the method uses nitric acid, melamine and cyanuric acid with relatively low price, forms a complex by utilizing intermolecular forces, introduces a proper amount of nitrate ions to cooperate with cyanuric acid molecules to influence the polymerization of precursor melamine, so that the heptazine ring structural unit is distorted, and g-C is realized 3 N 4 The lone pair electrons on the nitrogen atom can be excited by visible light, and the electrons are from n energy level to pi * Transition occurs, g-C is greatly improved 3 N 4 The material obtained by the method shortens the g-C of the material 3 N 4 The distance between molecular layers has relatively large specific surface area, and the shortened interlayer distance is favorable for electron conduction along pi-pi conjugation direction and electron transmission. The large specific surface area can provide a large number of active sites for the photocatalytic hydrogen evolution reaction. The ACCN obtained by the method does not contain toxic metal elements, has low manufacturing cost and can realize mass production.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of ACCN powder photocatalyst prepared in example three of the present invention.
In FIG. 2, curve 1 and curve 2 are, respectively, g-C prepared by conventional methods prepared in accordance with example III of the present invention 3 N 4 And the X-ray diffraction (XRD) pattern of ACCN photocatalyst prepared in accordance with the present invention
FIG. 3 is a graph 3 and a graph 4 showing ACCN prepared by the supermolecule self-assembly method and g-C prepared by the conventional method, respectively, according to the third embodiment of the present invention 3 N 4 Ultraviolet-visible absorption spectrum (UV-vis)
Fig. 5 is a graph comparing the effective light utilization of ACCN prepared in example three of the present invention and CCN prepared using conventional methods.
Fig. 6: is a Scanning Electron Microscope (SEM) picture of the ACCN powder photocatalyst prepared in example three of the present invention.
Detailed Description
The invention will now be further described with reference to examples, figures:
embodiment one:
step one, 1g of melamine is weighed and put into 75ml of concentrated nitric acid with the concentration of 68%, and stirred for 3 hours by a magnetic stirrer.
Step two, 60ml of deionized water and 20ml of absolute ethyl alcohol are measured and added into a 100ml beaker, and 3g of cyanuric acid is added and stirred for 30min.
And thirdly, filtering the melamine treated by the nitric acid in the first step by using filter paper, cleaning the melamine by using deionized water for three times, and adding the cleaned solid product into the cyanuric acid solution in the second step, and performing ultrasonic treatment for 60 minutes.
And fourthly, stirring the mixed solution in an oil bath at the temperature of 70 ℃ for 12 hours, and drying the mixed solution in a vacuum drying oven at the temperature of 80 ℃.
And fifthly, grinding the yellow brown precursor obtained in the step four, then placing the ground yellow brown precursor into a crucible, placing the crucible into a muffle furnace, heating to 530 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain light red powder, namely ACCN.
Embodiment two:
step one, 1.5g of melamine is weighed and put into 25ml of concentrated nitric acid with the concentration of 68%, and stirred for 2 hours by a magnetic stirrer.
Step two, 20ml of deionized water and 60ml of absolute ethyl alcohol are measured and added into a 100ml beaker, and 1g of cyanuric acid is added and stirred for 30min.
And thirdly, filtering the melamine treated by the nitric acid in the first step by using filter paper, washing the melamine with deionized water for three times, and adding the washed solid product into the cyanuric acid solution in the second step, and carrying out ultrasonic treatment for 40min.
And fourthly, stirring the mixed solution in an oil bath pot for 4 hours at the temperature of 90 ℃, and drying the mixed solution in a vacuum drying oven at the temperature of 80 ℃.
And fifthly, grinding the yellow brown precursor obtained in the step four, then placing the ground yellow brown precursor into a crucible, placing the crucible into a muffle furnace, heating to 540 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature to obtain light red powder, namely ACCN.
Embodiment III:
step one, weighing 2g of melamine, putting the melamine into 50ml of concentrated nitric acid with the concentration of 68%, and stirring the melamine for 1h by using a magnetic stirrer.
Step two, 40ml of deionized water and 40ml of absolute ethyl alcohol are measured and added into a 100ml beaker, and 2g of cyanuric acid is added and stirred for 30min.
And thirdly, filtering the melamine treated by the nitric acid in the first step by using filter paper, washing the melamine with deionized water for three times, and adding the washed solid product into the cyanuric acid solution in the second step, and performing ultrasonic treatment for 30min.
And fourthly, stirring the mixed solution in an oil bath pot for 5 hours at the temperature of 80 ℃, and drying the mixed solution in a vacuum drying oven at the temperature of 80 ℃.
And fifthly, grinding the yellow brown precursor obtained in the step four, then placing the ground yellow brown precursor into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat for 4 hours, and cooling to room temperature to obtain light red powder, namely ACCN.
Fig. 1 is a Transmission Electron Microscope (TEM) image of an ACCN photocatalyst prepared in example three of the present invention, in which the melamine agglomeration phenomenon without any modification is serious in the previous report, the morphology is unfavorable for electron transmission and active sites are difficult to be exposed, and as can be seen in the figure, the synthesized ACCN has no obvious agglomeration phenomenon, and the flaky ACCN is favorable for the migration of photo-generated carriers from the center to the surface of the sample, so that the recombination of the photo-generated carriers in the sample is avoided.
FIG. 3, curves 3 and 4, are ACCN prepared according to example III of the present invention and g-C prepared by conventional methods 3 N 4 The ultraviolet-visible light absorption spectrum (UV-vis) of the sample can be observed from the curve 4 that the sample does not absorb the visible light with the wavelength of more than 450nm, and the red graphite phase carbon nitride prepared by the method can absorb the visible light with the wavelength of 400nm to 650nm, so that the photocatalysis performance is greatly promoted.
FIG. 4 shows curves 5 and 6 of ACCN prepared according to example III of the present invention and g-C prepared by conventional methods 3 N 4 By comparing the photocatalytic hydrogen evolution performance of the catalyst, the red graphite phase carbon nitride can be seen to have improved photocatalytic hydrogen evolution rate, and the total hydrogen yield of 4 hours is g-C synthesized by the traditional method 3 N 4 4 times of (2). The reason for this is attributed to ACCN having excellent light absorption ability for visible light, a large specific surface area, and good carrier separation ability.
Fig. 5 is a graph comparing the effective light utilization of ACCN prepared in example three of the present invention and CCN prepared using conventional methods. The area of the shaded area in the figure represents the effective visible light of ACCN and CCN, which photons can directly excite the semiconductor photocatalyst to generate photogenerated carriers to participate in the photocatalytic reaction. Compared with CCN prepared by a traditional method, the effective absorbance of ACCN prepared by the third embodiment of the project is obviously improved by 2.18 times, which is very beneficial to improving the photocatalytic efficiency.
Fig. 6 is a Scanning Electron Microscope (SEM) picture of ACCN powder photocatalyst prepared in example three of the present invention. It can be seen that such flake-like carbon nitride can provide more active sites for the photocatalytic reaction, which is advantageous for the photocatalytic reaction to proceed.
Claims (9)
1. The preparation method of the red supermolecule graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light is characterized by comprising the following steps:
step 1: weighing melamine with the weight of 1-2 g, putting the melamine into concentrated nitric acid with the weight of 25-75 ml, and uniformly stirring;
step 2: filtering melamine treated by nitric acid in the step 1, washing the melamine with deionized water for a plurality of times to obtain a solid product, adding the solid product into cyanuric acid solution, and carrying out ultrasonic treatment;
the cyanuric acid solution is a mixed solution of 20-60 ml of deionized water, 20-60 ml of absolute ethyl alcohol and 1-3 g of cyanuric acid;
step 3: stirring the mixed solution in an oil bath at 70-90 ℃ for 4-12 hours, and then drying to obtain a yellow brown precursor;
step 4: grinding the yellow brown precursor, then placing the ground yellow brown precursor into a crucible, placing the crucible into a muffle furnace, heating to 530-550 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 2-4 h, and cooling to room temperature to obtain light red powder, namely ACCN.
The above ratio is a measure of preparing one part.
2. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: the concentration of the concentrated nitric acid is 68%.
3. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: the step 1 of stirring uniformly adopts a magnetic stirrer to stir for 1-3 h.
4. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: the filter paper is adopted for the filtration in the step 2.
5. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: and step 2, washing with deionized water three times.
6. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: and step 2, adding the solution into cyanuric acid solution, and performing ultrasonic treatment for 30-60 min.
7. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: the mixed solution of cyanuric acid is stirred for at least 30min when mixed.
8. The method for preparing the red supermolecular graphite phase carbon nitride photocatalyst for improving the utilization rate of visible light according to claim 1, which is characterized in that: and the step 3 is to put the materials into a vacuum drying oven to be dried at 75-90 ℃.
9. A red supramolecular graphite phase carbon nitride photocatalyst prepared by the method of any one of claims 1-8, characterized in that: the red supermolecular graphite phase carbon nitride ACCN catalyst has a molecular weight of 65.173m 2 A large specific surface area per g and promotes a lone pair electron at the nitrogen atom at n.fwdarw.pi * The absorption rate of visible light of 400nm-650nm is obviously improved by 2.18 times compared with CCN prepared by the traditional method.
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| US20170232427A1 (en) * | 2016-02-16 | 2017-08-17 | The George Washington University | Doped graphitic carbon nitrides, methods of making and uses of the same |
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