CN115385420A - In-situ controllable preparation method and application of phosphorus-doped carbon nitride electrode - Google Patents
In-situ controllable preparation method and application of phosphorus-doped carbon nitride electrode Download PDFInfo
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Abstract
The invention relates to an in-situ controllable preparation method and application of a phosphorus-doped carbon nitride electrode, which comprises the following steps: (1) Mixing a melamine solution and a phytic acid solution for supramolecular self-assembly reaction, separating after the reaction is completed, and drying to obtain a precipitate containing a phosphorus precursor; preparing a phosphorus-containing precursor dispersion liquid from the precipitate; (2) And uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of clean conductive glass, completely drying, sealing in a quartz tube, carrying out microwave heating reaction, and cooling after the reaction is finished to obtain the phosphorus-doped carbon nitride electrode. The phosphorus-doped carbon nitride electrode prepared by the invention has high yield and efficiency, the preparation method is simple, the degradation efficiency of the photoelectrocatalysis organic pollutants is high, and the degradation efficiency of the photoelectrocatalysis organic pollutants for degrading methylene blue for 30 minutes can reach 95%.
Description
Technical Field
The invention relates to the technical field of photoelectrodes, in particular to an in-situ controllable preparation method and application of a phosphorus-doped carbon nitride electrode.
Background
With the rapid development of fine chemical industry, pharmacy, printing and dyeing and other industries, a large amount of organic pollutant wastewater is generated, wherein organic dye is one of the important organic pollutants for detection and elimination in the polluted wastewater. Most organic dyes are known to be aromatic compounds, and the organic dyes enter organisms and human bodies to easily cause mutation of biomolecular structures, interfere normal life activities of the organisms and seriously affect the ecological environment and human health. However, the dye wastewater has complex components, high chromaticity, poor biodegradability and difficult degradation, so the treatment of the dye wastewater has great difficulty.
The main methods for treating dye wastewater at present comprise an adsorption method, a biological method and a chemical oxidation method, and the methods have incomplete organic dye removal effect, high requirements on process equipment and possibly cause secondary pollution. Therefore, the development of an economical and efficient remediation technology for organic dye pollution is urgently needed to solve the problem of increasingly serious wastewater pollution.
The photoelectrocatalysis has excellent performance as a new technology, and has obvious effect on degrading organic pollutants such as rhodamine B, methylene blue, methyl orange and the like. In recent years, the non-metal semiconductor polymer carbon nitride has the characteristics of unique energy band structure (2.7 eV), stable physicochemical properties, low price, easy obtainment and the like, so that the basic requirements of people on a photoelectric catalyst are met, and the morphology and the energy band structure of the carbon nitride are adjustable, therefore, the carbon nitride has great potential in the field of photoelectric degradation.
The conventional synthesis method of carbon nitride is to directly perform high-temperature thermal polymerization reaction on nitrogen-rich micromolecules (such as cyanamide, dicyanodiamine, melamine, urea and the like) serving as raw materials to obtain solid powder. The carbon nitride electrode prepared by using the solid powder has low stability and low photoelectric catalytic degradation efficiency due to few action sites and weak binding force between the material and the substrate. The in-situ preparation of the carbon nitride electrode is that nitrogen-rich raw materials are directly thermally polymerized on a substrate to form a carbon nitride film, so that the photoelectric conversion efficiency and the photoelectric catalytic degradation efficiency of the electrode can be improved to a certain extent. At present, methods for preparing carbon nitride electrodes in situ mainly include codeposition and vapor deposition. The codeposition method is to directly place the micromolecule solid raw material on the surface of the substrate to carry out in-situ thermal polymerization to form the carbon nitride electrode. The high temperature vapor deposition method is to place the substrate material inside the cover of the small molecule solid material thermal polymerization reactor and the gasified small molecules form carbon nitride film on the surface of the substrate. However, due to the limitation of small molecule raw materials and the thermal polymerization reaction region, the yield of carbon nitride electrodes prepared by the co-deposition method and the vapor deposition method is low, and the requirement of mass production cannot be met.
Therefore, how to further improve the yield of the in-situ prepared carbon nitride electrode and improve the electrode performance is a technical problem to be solved by the invention.
Disclosure of Invention
In order to solve the above technical problems, an in-situ controllable preparation method and application of a phosphorus-doped carbon nitride electrode are provided. The phosphorus-doped carbon nitride electrode prepared by the invention has the advantages of high yield, high efficiency, simple preparation method and high efficiency of degrading organic pollutants through photoelectrocatalysis.
An in-situ controllable preparation method of a phosphorus-doped carbon nitride electrode comprises the following steps:
(1) Mixing a melamine solution and a phytic acid solution for supramolecular self-assembly reaction, separating after the reaction is completed, and drying to obtain a precipitate containing a phosphorus precursor;
preparing phosphorus-containing precursor dispersion liquid by using the precipitate;
(2) And uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of clean conductive glass, completely drying, sealing in a quartz tube, carrying out microwave heating reaction, and cooling after the reaction is finished to obtain the phosphorus-doped carbon nitride electrode.
Further, the solvent in the melamine solution is one of secondary water, dimethyl sulfoxide, DMF and ethylene glycol, preferably secondary water; the temperature of the supermolecule self-assembly reaction is 30-80 ℃, and the reaction time is 3-12h.
Further, the concentration of the phosphorus-containing precursor dispersion liquid is 0.1-20mg/mL, preferably 1.0-10mg/mL; the phosphorus-containing precursor dispersion liquid is coated on the conductive glass in an amount of 0.2-1 μ L/mm 2 Preferably, the coating amount is 0.3 to 0.6. Mu.L/mm 2 。
Further, the solvent in the phosphorus-containing precursor dispersion liquid is an ethanol-water solution, wherein the volume ratio of ethanol to distilled water is 1.
Further, the complete drying process comprises naturally airing at room temperature for 3-12h, and then drying at 60-80 ℃ to constant weight. The natural drying at room temperature is to make the solvent in the dispersion naturally volatilize at low temperature to ensure the uniformity of the phosphorus-containing precursor on the conductive glass.
Furthermore, the microwave heating reaction is carried out under the protection of inert gas, the heating temperature is 200-300 ℃, the heating time is 10-50s, the microwave power is 500-800W, and the frequency is 2450MHz.
Furthermore, the thickness of the phosphorus-doped carbon nitride in the phosphorus-doped carbon nitride electrode is 1-2 microns, and the load capacity of the phosphorus-doped carbon nitride is 0.6-7 mu g/cm 2 。
The invention also provides application of the phosphorus-doped carbon nitride electrode prepared by the preparation method in photoelectrocatalysis degradation of organic dye, wherein the organic dye is methylene blue.
The beneficial technical effects are as follows:
the invention prepares a phosphorus-doped carbon nitride electrode by an in-situ method, and the phosphorus-doped carbon nitride electrode is a phosphorus-doped carbon nitride film formed by directly thermally polymerizing a nitrogen-rich raw material and a doped phosphorus source self-assembly body on a substrate. As the supermolecule self-assembly body undergoes the processes of in-situ nucleation, growth and crystallization on the surface of the substrate, the interaction force between the prepared phosphorus-doped carbon nitride and the substrate is stronger, the photoelectric property of the electrode is more stable, and the electrode has higher photoelectric conversion efficiency and photoelectric catalytic degradation efficiency.
(1) According to the phosphorus-doped carbon nitride in-situ preparation method, the phosphorus-containing precursor formed by self-assembly of the nitrogen-rich micromolecules and the phosphorus-containing micromolecules is modified on the surface of the FTO, and the phosphorus-doped carbon nitride electrode is obtained by utilizing microwave rapid in-situ thermal polymerization, so that the preparation efficiency of the electrode can be greatly improved; in addition, the invention takes the closed quartz tube as the reactor for preparing the electrode in situ, so that the thermal polymerization reaction area is reduced, and the yield of preparing the electrode by the in situ method can be greatly improved. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode can prepare at least 200 electrodes in 1 minute in a 20L microwave oven, has high preparation efficiency and preparation yield, and is suitable for industrial mass production.
(2) In the in-situ controllable preparation of the phosphorus-doped carbon nitride electrode, the molecular composition, the structural morphology and the carbon nitride amount of the phosphorus-doped carbon nitride electrode are regulated and controlled by doping phosphorus atoms and controlling the phosphorus-containing precursor amount, so that the photoelectric conversion performance and the photoelectric catalytic performance of the electrode are further improved.
Drawings
FIG. 1 is a schematic diagram of an FTO modified by a phosphorus-containing precursor and a phosphorus-doped carbon nitride electrode in example 1, wherein A represents the FTO modified by the phosphorus-containing precursor and B represents the phosphorus-doped carbon nitride electrode.
Fig. 2 is an XRD pattern of the phosphorus-doped carbon nitride electrode of example 1 and the phosphorus-doped carbon nitride powder of comparative example 2, wherein a represents the phosphorus-doped carbon nitride electrode and b represents the phosphorus-doped carbon nitride powder.
Fig. 3 is an SEM image of the phosphorus-doped carbon nitride electrode of example 1, wherein B is a partial enlarged view of a.
FIG. 4 is an SEM photograph of the phosphorus-doped carbon nitride electrode obtained in examples 1-3, wherein A represents a concentration of 1mg/mL using a phosphorus-containing precursor dispersion (example 2), B represents a concentration of 5mg/mL using a phosphorus-containing precursor dispersion (example 1), and C represents a concentration of 10mg/mL using a phosphorus-containing precursor dispersion (example 3).
FIG. 5 is a graph showing the photoelectric conversion test of the phosphorus-doped carbon nitride electrodes of examples 1 to 3. Wherein a represents that the concentration of the phosphorus-containing precursor dispersion is 1mg/mL (example 2), b represents that the concentration of the phosphorus-containing precursor dispersion is 5mg/mL (example 1), and c represents that the concentration of the phosphorus-containing precursor dispersion is 10mg/mL (example 3).
FIG. 6 is a comparison of the photoelectric properties of the phosphorus-doped carbon nitride electrode prepared by the in-situ method of example 1 and the phosphorus-doped carbon nitride electrode prepared by the ex-situ method of comparative example 2.
Fig. 7 is a comparison of the photoelectric properties of the phosphorus-doped carbon nitride electrode of example 1 and the phosphorus-free doped carbon nitride electrode of comparative example 1.
Fig. 8 is a graph of the stability of the phosphorus doped carbon nitride electrode of example 1.
Fig. 9 is a graph showing the degradation rate of methylene blue catalytically degraded by the photoelectrode of example 1, comparative example 1 and comparative example 2, and the lower left insert is a photograph showing the solution before and after the methylene blue is degraded by the phosphorus-doped carbon nitride electrode of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods, for which specific conditions are not noted in the following examples, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
An in-situ controllable preparation method of a phosphorus-doped carbon nitride electrode comprises the following steps:
(1) Weighing 0.5g of melamine solid, placing the melamine solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent melamine solution;
at the constant temperature of 60 ℃, 200mL of melamine solution and 1.0mL of 70% phytic acid solution are mixed, and magnetic stirring is carried out to carry out supermolecule self-assembly reaction for 6h, so that the melamine and the phytic acid are fully reacted, and a phosphorus-containing precursor precipitate is completely formed;
standing the suspension of the phosphorus-containing precursor precipitate at room temperature for 3h for settling, then removing most of the solvent by centrifugal separation, and drying in a drying oven at 80 ℃ for 24h to obtain a dried phosphorus-containing precursor precipitate;
preparing phosphorus-containing precursor precipitate into 5mg/mL phosphorus-containing precursor dispersion liquid, wherein a solvent in the dispersion liquid is ethanol and distilled water which are mixed according to a volume ratio of 1;
(2) Cutting the FTO conductive glass into 50 x 10mm by using a cutting machine, respectively placing the FTO conductive glass into acetone, absolute ethyl alcohol and 0.1mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 15min by using an ultrasonic cleaning instrument with 480W power, completely washing the FTO conductive glass with distilled water, and then placing the FTO conductive glass into a drying oven with 60 ℃ for drying to obtain clean FTO for later use; the conductive surface of the FTO is fixed by the insulating tape to form a 15 multiplied by 10mm area (the area is 150 mm) 2 )；
Measuring 50 mu L of the phosphorus-containing precursor dispersion liquid, uniformly coating the dispersion liquid on the surface of FTO, standing at room temperature for 12h, removing the insulating tape, and drying at 80 ℃ for 3h to obtain a phosphorus-containing precursor modified FTO, wherein the physical diagram of the FTO is shown as A in figure 1;
and (2) tightly wrapping an FTO area which is not modified by the phosphorus-containing precursor by using tin foil paper, placing the FTO in a quartz tube with a matched size, sealing the opening of the quartz tube by using an aluminum cover, then placing the quartz tube into a microwave oven for microwave heating reaction, wherein the heating temperature is 250, the heating time is 30s, the microwave power is 700W, the frequency is 2450MHz, cooling to room temperature after the reaction is finished, taking out the FTO, and removing the tin foil paper to obtain the phosphorus-doped carbon nitride electrode, wherein the thickness of the phosphorus-doped carbon nitride is 1.5 microns, and the material diagram of the phosphorus-doped carbon nitride electrode is shown as B in figure 1.
The modification amount of phosphorus-doped carbon nitride calculated according to the mass of FTO in this example is 5 mug.
Example 2
An in-situ controllable preparation method of a phosphorus-doped carbon nitride electrode comprises the following steps:
(1) Weighing 0.5g of melamine solid, placing the melamine solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent melamine solution;
at the constant temperature of 60 ℃, mixing 200mL of melamine solution with 1.0mL of 70% phytic acid solution, and carrying out a supermolecule self-assembly reaction for 6h by magnetic stirring to ensure that the melamine and the phytic acid fully react to completely form phosphorus-containing precursor precipitate, wherein the self-assembly precursor is precipitated from the solution due to large molecular weight so that the reaction solution is a suspension;
standing the suspension of the phosphorus-containing precursor precipitate at room temperature for 3h for settling, then removing most of the solvent by centrifugal separation, and drying in a drying oven at 80 ℃ for 24h to obtain a dried phosphorus-containing precursor precipitate;
preparing a phosphorus-containing precursor precipitate into 1mg/mL phosphorus-containing precursor dispersion liquid, wherein a solvent in the dispersion liquid is ethanol and distilled water which are mixed according to a volume ratio of 1;
(2) Cutting the FTO conductive glass into 50 x 10mm by using a cutting machine, respectively placing the FTO conductive glass in acetone, absolute ethyl alcohol and 0.1mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 15min by adopting an ultrasonic cleaning instrument with 480W power, completely washing the FTO conductive glass by using distilled water, and then placing the FTO conductive glass into a drying oven at 60 ℃ for drying to obtain clean FTO for later use; the conductive surface of the FTO is fixed by the insulating tape to form a 15 multiplied by 10mm area (the area is 150 mm) 2 )；
Weighing 50 mu L of the phosphorus-containing precursor dispersion liquid, uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of FTO, standing at room temperature for 12 hours, removing the insulating tape, and drying at 80 ℃ for 3 hours;
tightly wrapping an FTO area which is not modified by the phosphorus-containing precursor by using tin foil paper, placing the FTO in a quartz tube with matched size, sealing the opening of the quartz tube by using an aluminum cover, then placing the quartz tube into a microwave oven for microwave heating reaction at the heating temperature of 250 for 30s, the microwave power of 700W and the frequency of 2450MHz, cooling to room temperature after the reaction is finished, taking out the FTO, and removing the tin foil paper to obtain the phosphorus-doped carbon nitride electrode, wherein the thickness of the phosphorus-doped carbon nitride is 1 micron.
In this example, the modification amount of the phosphorus-doped carbon nitride was 1. Mu.g, calculated based on the mass of FTO.
Example 3
An in-situ controllable preparation method of a phosphorus-doped carbon nitride electrode comprises the following steps:
(1) Weighing 0.5g of melamine solid, placing the melamine solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent melamine solution;
at the constant temperature of 60 ℃, 200mL of melamine solution and 1.0mL of 70% phytic acid solution are mixed, and magnetic stirring is carried out to carry out supermolecule self-assembly reaction for 6h, so that the melamine and the phytic acid are fully reacted, and a phosphorus-containing precursor precipitate is completely formed;
standing the suspension of the phosphorus-containing precursor precipitate at room temperature for 3h for settling, then removing most of the solvent by centrifugal separation, and drying in a drying oven at 80 ℃ for 24h to obtain a dried phosphorus-containing precursor precipitate;
preparing a phosphorus-containing precursor precipitate into 10mg/mL phosphorus-containing precursor dispersion liquid, wherein a solvent in the dispersion liquid is ethanol and distilled water which are mixed according to a volume ratio of 1;
(2) Cutting FTO conductive glass into 50 × 10mm size with a cutting machine, respectively placing in acetone, anhydrous ethanol, 0.1mol/L sodium hydroxide solution, and adopting 480WCarrying out ultrasonic cleaning for 15min by using a power ultrasonic cleaning instrument, completely washing the FTO by using distilled water, and then putting the FTO into a 60-DEG C drying oven for drying to obtain clean FTO for later use; the conductive surface of the FTO is fixed by the insulating tape to form a 15 multiplied by 10mm area (the area is 150 mm) 2 )；
Weighing 50 mu L of the phosphorus-containing precursor dispersion liquid, uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of FTO, standing at room temperature for 12 hours, removing the insulating tape, and drying at 80 ℃ for 3 hours;
and (2) tightly wrapping an FTO area which is not modified by the phosphorus-containing precursor by using tin foil paper, placing the FTO in a quartz tube with a matched size, sealing the opening of the quartz tube by using an aluminum cover, then placing the quartz tube into a microwave oven for microwave heating reaction at the heating temperature of 250 for 30s, the microwave power of 700W and the frequency of 2450MHz, cooling to room temperature after the reaction is finished, taking out the FTO, and removing the tin foil paper to obtain the phosphorus-doped carbon nitride electrode, wherein the thickness of the phosphorus-doped carbon nitride is 2 microns.
The modification amount of phosphorus-doped carbon nitride calculated according to the mass of FTO in this example is 10 mug.
Comparative example 1
Preparing a phosphorus-free doped carbon nitride electrode:
(1) Weighing 0.5g of melamine solid, placing the melamine solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent melamine solution;
weighing 0.5g of cyanuric acid solid, placing the cyanuric acid solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent cyanuric acid solution;
mixing 200mL of melamine solution and cyanuric acid solution at the constant temperature of 60 ℃, performing supermolecule self-assembly for 6h by magnetic stirring, ensuring that the melamine and cyanuric acid fully react to completely form a phosphorus-free precursor precipitate, standing at room temperature for 3h for settling, removing most of solvent by centrifugal separation, and drying in a drying oven at the temperature of 80 ℃ for 24h to obtain a dried phosphorus-free precursor precipitate;
the phosphorus-free precursor is precipitated to prepare 5mg/mL phosphorus-free precursor dispersion liquid, the solvent in the dispersion liquid is ethanol and distilled water which are mixed according to the volume ratio of 1;
(2) Cutting the FTO conductive glass into 50 x 10mm by using a cutting machine, respectively placing the FTO conductive glass into acetone, absolute ethyl alcohol and 0.1mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 15min by using an ultrasonic cleaning instrument with 480W power, completely washing the FTO conductive glass with distilled water, and then placing the FTO conductive glass into a drying oven with 60 ℃ for drying to obtain clean FTO for later use; the conductive surface of the FTO is fixed by an insulating tape to form a 15 multiplied by 10mm area (the area is 150 mm) 2 )；
Weighing 50 mu L of the phosphorus-containing precursor dispersion liquid, uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of FTO, standing at room temperature for 12 hours, removing the insulating tape, and drying at 80 ℃ for 3 hours;
and (3) tightly wrapping an FTO area which is not modified by the phosphorus-containing precursor by using tin foil paper, placing the FTO in a quartz tube with a matched size, sealing the opening of the quartz tube by using an aluminum cover, then placing the quartz tube into a microwave oven for microwave heating reaction, wherein the reaction parameters are consistent with those of the example 1, and obtaining the phosphorus-free doped carbon nitride electrode, wherein the thickness of the carbon nitride is 1.5 microns.
Comparative example 2
Preparing a phosphorus-doped carbon nitride powder directly modified electrode:
(1) Weighing 0.5g of melamine solid, placing the melamine solid in a 500mL clean beaker, adding 200mL of distilled water, adjusting the temperature to 60 ℃, and magnetically stirring for 60min to obtain a clear and transparent melamine solution;
mixing 200mL of melamine solution and 1.0mL of 70% phytic acid solution at the constant temperature of 60 ℃, performing magnetic stirring to perform supramolecular self-assembly for 6 hours to ensure that the melamine and the phytic acid are fully reacted to completely form phosphorus-containing precursor precipitate, standing at room temperature for 3 hours to perform sedimentation, removing most of solvent through centrifugal separation, drying in a drying oven at the temperature of 80 ℃ for 24 hours to ensure complete drying of the solvent to obtain dried phosphorus-containing precursor precipitate;
placing the dried phosphorus-containing precursor into a 30mL crucible, covering the crucible with a cover, placing the crucible into a microwave oven for microwave heating reaction, keeping the reaction parameters consistent with those of the embodiment 1, and cooling to room temperature to obtain phosphorus-doped carbon nitride powder;
preparing 1mg/mL phosphorus-doped carbon nitride dispersion liquid from phosphorus-doped carbon nitride powder, mixing ethanol and distilled water in the volume ratio of 1;
(2) Cutting the FTO conductive glass into 50 x 10mm by using a cutting machine, respectively placing the FTO conductive glass in acetone, absolute ethyl alcohol and 0.1mol/L sodium hydroxide solution, carrying out ultrasonic cleaning for 15min by adopting an ultrasonic cleaning instrument with 480W power, completely washing the FTO conductive glass by using distilled water, and then placing the FTO conductive glass into a drying oven at 60 ℃ for drying to obtain clean FTO for later use; the conductive surface of the FTO is fixed by the insulating tape to form a 15 multiplied by 10mm area (the area is 150 mm) 2 )；
And measuring 10 mu L of the phosphorus-containing precursor dispersion liquid, uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of FTO, standing at room temperature for 12 hours, removing the insulating tape, and drying at 80 ℃ for 3 hours to obtain the photoelectrode directly modified by phosphorus-doped carbon nitride powder.
Performance testing
The phosphorus-doped carbon nitride electrode of example 1 and the phosphorus-doped carbon nitride Powder of comparative example 2 were subjected to XRD measurements and analyzed using an X' Pert Powder type X-ray diffractometer. The instrument test conditions were set as: radiation having a wavelength of
The scanning range is 10 degrees to 80 degrees, the scanning speed is set to be 5 degrees/min, the voltage value is 40KV, and the current value is 40mA. The XRD spectrum is shown in fig. 2, in which 2 θ represents the angle between X-ray and scattered ray, and the ordinate represents diffraction intensity, wherein a represents a phosphorus-doped carbon nitride electrode, and b represents a phosphorus-doped carbon nitride powder. As can be seen from fig. 2, the XRD peaks of the phosphorus doped carbon nitride prepared by the two methods are similar, indicating that their structures are not very different. Wherein the 002 crystal plane (27.4 °) of the phosphorus-doped carbon nitride powder is slightly larger than that of the phosphorus-doped carbon nitride electrode (26.6 °), which may cause test errors due to different test substrates.
The SEM topography of the phosphorus-containing precursor-modified FTO and the final product phosphorus-doped carbon nitride electrode of example 1 is shown in fig. 3, and it can be seen from fig. 3 that the supramolecular self-assembly of melamine and phytic acid in the phosphorus-containing precursor-modified FTO is fibrous, and the morphology after the in-situ method converts the supramolecular self-assembly into the phosphorus-doped carbon nitride optical electrode is still fibrous, and the surface has a large area porosity.
Photoelectric conversion tests were performed on the photoelectrodes of the above examples and comparative examples. An electrochemical three-electrode system is adopted, and the photoelectrode of the above embodiment and the comparative example is respectively used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a silver/silver chloride electrode is used as a reference electrode. The front surface of the working electrode faces to an incident light source, a xenon lamp is used as an incident light source generator, the electrochemical workstation selects a current-time detection method in 0.1mol/L KCl electrolyte solution, and the constant potential is set to be 0V. Controlling the opening and closing time of the light-shielding shutter to be 20s in the scanning process, and recording a current-time relation curve, wherein a photoelectric conversion test curve chart of the phosphorus-doped carbon nitride electrode of the embodiments 1 to 3 is shown in fig. 5; example 1 the photoelectric properties of the in-situ method for preparing a phosphorus-doped carbon nitride electrode and the ex-situ method for preparing a phosphorus-doped carbon nitride electrode of comparative example 2 are shown in fig. 6; the photoelectric performance plots of the phosphorus-doped carbon nitride electrode of example 1 and the phosphorus-free doped carbon nitride electrode of comparative example 1 are shown in fig. 7. The average values of the charging current and the photocurrent were compared, and the results are shown in fig. 5 to 7 and table 1.
The photoelectrode of the above example and comparative example was subjected to a test of photoelectric stability. The photoelectrode of the embodiment and the comparative example is placed in an electrochemical three-electrode system, the electrochemical workstation selects a current-time detection method, a current-time relation curve with the number of the open and close of the shading shutter being 10 times is recorded, the difference value of the average value of the single charging current and the average value of the photocurrent is taken, and the RSD is calculated. The stability profile of the phosphorus doped carbon nitride electrode of example 1 is shown in fig. 8. The results are shown in Table 1 above.
TABLE 1 photoelectric Properties of photoelectrodes of examples and comparative examples
As can be seen from fig. 5 to 7 and table 1, the photocurrent values of the phosphorus-doped carbon nitride electrode prepared in situ in example 1 were 1.77 and 115.7 times those of the phosphorus-doped carbon nitride powder coating prepared in comparative example 2 and the phosphorus-free doped carbon nitride electrode prepared in situ in comparative example 1.
As can be seen from fig. 8 and table 1, the RSD of the phosphorus-doped carbon nitride electrode prepared by the in-situ controllable method of the present invention is not more than 1.5%, which indicates that the photoelectric stability of the phosphorus-doped carbon nitride electrode prepared in-situ by the present invention is good.
Application example 1
The photoelectrode of the above examples and comparative examples was used for catalytic degradation of methylene blue.
An electrochemical three-electrode system is adopted, the photoelectricity electrodes of the above examples and comparative examples are used as working electrodes, the platinum sheet electrode is used as a counter electrode, and the silver/silver chloride electrode is used as a reference electrode. Different electrodes are respectively placed in the wastewater polluted by the methylene blue, and the electrochemical workstation selects a constant potential method and sets the constant potential to be +0.2V. Before the start of the photoelectrocatalysis degradation, the solution is magnetically stirred for 10min in a dark place, after the photoelectrode and the wastewater containing methylene blue fully act, 1.0mL of reaction solution is filtered by a 0.22 micron needle filter, and the filtrate is placed into a brown centrifuge tube for label preservation. Continuing magnetic stirring, starting circulating cooling water, and keeping the temperature of the reaction solution at 15-25 ℃. After a 300W xenon lamp and an electrochemical workstation are turned on, 1.0mL of reaction solution is taken every 5min, filtered and placed into a centrifuge tube for label preservation until the color of the reaction solution is not changed by visual observation.
Preparing different methylene blue standard solutions of 0.10mg/L, 1.0mg/L, 10mg/L, 20mg/L, 30mg/L, 40 mg/L and 50mg/L, measuring the absorbance of the methylene blue standard solution at 665nm by using an ultraviolet visible absorption photometer, and drawing a relation curve between the absorbance and the concentration, namely a working curve. And fitting the working curve to obtain a fitting equation. Measuring the absorbance of the reaction solution degraded at different time, and calculating to obtain the concentration (C) of methylene blue in the wastewater subjected to photoelectric degradation at different time according to a fitting equation t ). The degradation efficiency calculation formula of the method is as follows:
degradation efficiency = (C) 0 -C t /C 0 ) X 100% where C 0 Represents the concentration of methylene blue (10 mg/mL), C, in the initial wastewater t Indicating the concentration of methylene blue in the wastewater after different times of photodegradation.
The degradation rate of the photoelectrode of example 1 and comparative examples 1-2 for catalytically degrading methylene blue is shown in fig. 9 and table 2.
TABLE 2 degradation rates of photoelectrode catalyzed degradation of methylene blue in examples and comparative examples
As can be seen from fig. 9 and table 2, the in situ phosphorus doped carbon nitride electrode of example 1 degraded methylene blue to 95% efficiency for 30 minutes.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. An in-situ controllable preparation method of a phosphorus-doped carbon nitride electrode is characterized by comprising the following steps:
(1) Mixing a melamine solution and a phytic acid solution for supermolecule self-assembly reaction, separating after the reaction is completed, and drying to obtain a precipitate containing a phosphorus precursor;
preparing phosphorus-containing precursor dispersion liquid by using the precipitate;
(2) And uniformly coating the phosphorus-containing precursor dispersion liquid on the surface of clean conductive glass, completely drying, sealing in a quartz tube, carrying out microwave heating reaction, and cooling after the reaction is finished to obtain the phosphorus-doped carbon nitride electrode.
2. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode according to claim 1, wherein the solvent in the melamine solution is one of secondary water, dimethyl sulfoxide, DMF and ethylene glycol; the temperature of the supramolecular self-assembly reaction is 30-80 ℃, and the reaction time is 3-12h.
3. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode according to claim 1, wherein the concentration of the phosphorus-containing precursor dispersion is 0.1-20mg/mL; the coating amount of the phosphorus-containing precursor dispersion liquid on the conductive glass is 0.2-1 mu L/mm 2 。
4. The method as claimed in claim 1, wherein the solvent in the phosphorus-containing precursor dispersion is an ethanol-water solution, wherein the volume ratio of ethanol to distilled water is 1.
5. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode according to claim 1, wherein the complete drying process comprises natural air drying at room temperature for 3-12h, and then drying at 60-80 ℃ to constant weight.
6. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode as claimed in claim 1, wherein the microwave heating reaction is carried out under the protection of inert gas, the heating temperature is 200-300 ℃, the heating time is 10-50s, the microwave power is 500-800W, and the frequency is 2450MHz.
7. The in-situ controllable preparation method of the phosphorus-doped carbon nitride electrode according to claim 1, wherein the thickness of the phosphorus-doped carbon nitride in the phosphorus-doped carbon nitride electrode is 1-2 microns, and the loading amount of the phosphorus-doped carbon nitride is 0.6-7 μ g/cm 2 。
8. The application of the phosphorus-doped carbon nitride electrode prepared by the preparation method according to any one of claims 1 to 7 in photoelectrocatalytic degradation of organic dyes.
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