CN111962083A - Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection - Google Patents
Graphite-phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection Download PDFInfo
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Abstract
The invention discloses a graphite phase carbon nitride @ graphene composite film photoanode for photoproduction cathode protection, wherein the graphite phase carbon nitride is a carbon nitride nanotube, and the graphene is a graphene roll. The invention also discloses a preparation method of the composite film photo-anode, which comprises the following steps: 1) and calcining melamine by using stage heating to prepare the graphite-phase carbon nitride nanotube. 2) Ultrasonically dispersing the carbon nitride nanotube and graphene oxide in deionized water, carrying out quenching treatment on the dispersion liquid by taking liquid nitrogen as a medium, and carrying out freeze drying to obtain the carbon nitride nanotube coated by the graphene oxide. 3) Depositing the graphite-phase carbon nitride nanotube and graphene oxide on FTO conductive glass by an electrophoretic deposition method, and calcining for a certain time at a certain temperature to obtain the graphite-phase carbon nitride and graphene composite membrane photoelectrode. The photoelectrode prepared by the method has excellent photoelectron transmission capability and photoproduction cathode protection performance.
Description
Technical Field
The invention relates to a graphite-phase carbon nitride @ graphene composite film photoanode and a preparation method thereof, in particular to a graphene roll-coated graphite-phase carbon nitride nanotube photoelectrode, a preparation method thereof and application thereof as a photoanode in photoproduction cathode protection.
Background
The photoelectrochemical cathodic protection utilizes the photovoltaic effect of a semiconductor, and photo-generated electrons are generated by excitation under illumination and are supplied to coupled metal to cause negative potential shift of the metal, andis lower than the self-corrosion potential, thereby protecting the metal. Graphite phase carbon nitride (g-C)3N4) The semiconductor is a typical non-metal semiconductor, has stable chemical property, narrow forbidden band (2.7 eV), can respond to visible light, has low cost and easy preparation, and gradually draws attention in the field of photoelectrochemical cathode protection. But block g-C3N4Has small specific surface area, less active sites, lower electron mobility and insufficient photogenerated hole oxidation capacity, so the application in the field of photoelectrochemical cathode protection is limited. For g-C3N4The morphology is regulated, and the structural property and the photoelectric property of the material are hopefully enhanced.
Construction of heterojunction and element doping expected to improve g-C3N4Photoelectrochemical properties of (a). g-C3N4@ ZnO shell-core Structure, C3N4@In2O3Quasi-shell-core nanocomposites, by C3N4And ZnO, In2O3An effective heterojunction electric field is formed on the interface between the two electrodes, so that the separation efficiency of the photo-generated electron-hole pair is improved; co-doped g-C3N4Change g-C3N4The energy band structure of (1) enlarges g-C3N4Light absorption range of (1). However, the presence of metallic elements in the composite material risks secondary pollution to the environment during application.
The graphene is a lamellar structure material formed by single-layer carbon atoms, has large specific surface area and is a good electron acceptor; meanwhile, graphene is an ideal conductor with zero forbidden band, and a carrier has good mobility in a graphene film. Thus, graphene modified C3N4The advantages are obvious. However, only by g-C3N4The graphene is simply compounded, so that the utilization rate of the obtained composite material on visible light and the improvement on the photoproduction electron-hole separation efficiency are limited. Therefore, it is necessary to use from g-C3N4Starting from the device, performing shape regulation and control such as one-dimensional and ultra-thin shapes and the like on the device so as to increase photoelectrochemical reaction active sites; researching a method for constructing an effective heterojunction with graphene to adjust an energy band structure of the graphene so as to expand a light absorption range; at the same timeThe good flexibility of the graphene is utilized to realize the C-pair3N4The surface coating of the composite material enriches the conduction path of electrons and improves the protection performance of photoelectrochemistry cathodes.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a graphite-phase carbon nitride nanotube @ graphene composite film photo-anode, wherein the composite film photo-anode has a photo-induced cathodic protection effect on metal.
The second technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method of the graphite phase carbon nitride nanotube @ graphene composite film photo-anode, which is simple in process, economical and practical and convenient for large-scale preparation.
In order to solve the first technical problem, the invention adopts the following technical scheme:
the utility model provides a graphite phase carbon nitride @ graphene composite film photoanode, graphite phase carbon nitride is the nanotube, graphite alkene is the graphite alkene book.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a preparation method of a graphite-phase carbon nitride nanotube @ graphene comprises the following steps:
(1) grinding melamine powder, placing the ground melamine powder into a corundum ark, carrying out medium-speed oscillation treatment for 5-20min, covering the corundum ark, moving the corundum ark into a tube furnace, heating the corundum ark to 500 ℃ at a speed of 10 ℃/min under a protective atmosphere, calcining the corundum ark for 2h, heating the corundum ark to 530 ℃ at a speed of 1 ℃/min, calcining the corundum ark for 2h, and naturally cooling the corundum ark to obtain a carbon nitride nanotube;
(2) sequentially adding graphene oxide powder and carbon nitride nanotubes into deionized water, and carrying out ultrasonic treatment for 1-2 h to uniformly mix; transferring the obtained dispersion liquid into a plastic centrifuge tube, heating for 10min, then quickly placing the dispersion liquid into liquid nitrogen, and carrying out freeze drying to obtain a graphene oxide coated carbon nitride nanotube;
(3) ultrasonically dispersing the powder obtained in the step (2) in acetone, and then adding a certain amount of iodine to obtain electrolyte; depositing the carbon nitride nanotube coated by the graphene oxide on the surface of the FTO conductive glass by adopting an electrophoretic deposition method and taking the FTO conductive glass as a negative electrode and a platinum sheet as a positive electrode, and naturally drying;
(4) and transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, roasting for 1h in a protective atmosphere, and cooling to room temperature to obtain the graphite-phase carbon nitride @ graphene composite membrane photoanode.
Preferably, the apparatus used in the shaking treatment in step (1) is an SHZ-82 air constant temperature table type shaker, and the protective atmosphere is nitrogen.
Preferably, the graphene oxide in the step (2) is prepared by a modified Hummers method.
Further, the mass ratio of the carbon nitride nanotubes to the graphene oxide in the step (2) is 1: 3-3: 1, the ultrasonic power is 400-800W, and the heating temperature is 60-100 ℃.
Preferably, the concentration of the carbon nitride nanotube @ graphene oxide powder in the step (3) is 0.2 g/L.
Preferably, the mass ratio of the powder to the iodine in the step (3) is 2: 1.
Further, the electrophoretic deposition voltage in the step (3) is 20V, and the deposition time is 10 min.
Preferably, the protective atmosphere in the step (4) is argon, the roasting temperature is 350 ℃, and the heating rate is 2 ℃/min.
The application of the graphite-phase carbon nitride @ graphene composite film photoanode in the field of photoproduction cathode protection in claim 1.
The basic principle of the invention is as follows: c3N4After being compounded with graphene, under the irradiation of visible light, C3N4The valence band electron absorbs the photon excited transition to the conduction band, generating a photo-generated electron-hole pair, the photo-generated electron from C3N4The conduction band transits to the graphene film and then migrates to the surface of the metal to be protected connected with the graphene film to generate photoproduction current, so that the metal is subjected to cathodic polarization, the electrode potential is reduced and is far lower than the natural corrosion potential of the metal, and the metal is protected by the cathode to avoid corrosion. At the same time, holes are drawn from C3N4The valence band is transferred to the graphene, thereby effectively realizing the separation of electrons and holes and overcoming the problem of poor photoproduction cathode protection effect of a single carbon nitride filmTo give a title.
The invention develops an advanced coating preparation technology to obtain the carbon nitride composite film with good cathodic protection effect on metal. According to the invention, a carbon nitride nanotube and graphene oxide composite powder material is obtained by combining roasting with an quenching technology, and then deposited on FTO conductive glass by an electrophoresis method, so that a carbon nitride nanotube and graphene oxide composite film photo-anode is obtained. The photo-anode is soaked in electrolyte solution and connected with the 304 stainless steel to be protected, and the photo-anode can play a role in photo-cathode protection under illumination.
The invention has the advantages that: according to the method, the shape control of carbon nitride is combined with graphene modification, the coating of the carbon nitride by the graphene oxide roll is completed through a quenching technology, the reduction of the graphene oxide is realized by combining an electrophoretic deposition-thermal reduction technology, and the carbon nitride nanotube @ graphene photoelectrode is synchronously obtained. The hollowing of the carbon nitride and the introduction of the graphene improve the utilization efficiency of the carbon nitride to visible light; the surface coating of the graphene promotes the close contact between the carbon nitride and the graphene and the construction of an effective heterojunction; the one-dimensional carbon nitride and the formation of a heterojunction can effectively promote the transfer of electrons and reduce the recombination of photon-generated carriers, thereby improving the protection effect of the composite film on 304 stainless steel.
The carbon nitride nanotube @ graphene composite film prepared by the method has the advantages of stable structure, complete and uniform coating layer and good photoelectrochemical property. The synergistic effect between the one-dimensional tubular structure of the carbon nitride and the reduced graphene oxide endows the photo-anode with the capability of greatly reducing the electrode potential of the metal coupled with the photo-anode during illumination. The results show that the composite membrane is prepared by adding NaOH-Na2In the S mixed solution, when visible light irradiates, the electrode potential of the 304 stainless steel which is connected with the S mixed solution and is immersed in 3.5 percent NaCl solution can be reduced to minus 550mV which is far lower than the natural corrosion potential of the stainless steel, which shows that the cathode protection effect of the composite membrane is obvious, and the S mixed solution has wide application prospect in the field of photo-generated cathode protection.
Drawings
FIG. 1 is an XRD diffraction pattern of a sample prepared by an embodiment of the invention, (a) g-C3N4,(b) g-C3N4-NTs, (c) g-C3N4@RGO,(d) g-C3N4-NTs @RGO。
FIG. 2 shows graphite-phase carbon nitride @ graphene (g-C) according to an embodiment of the present invention3N4-NTs @ RGO) surface topography of the composite membrane.
Fig. 3 is an XPS curve of the prepared graphite-phase carbon nitride @ graphene according to an embodiment of the present invention, wherein (a) is a total spectrum; (B) high resolution C1s maps; (C) high resolution N1s spectrum; (D) an O1s spectrum. (a) g-C3N4,(b) g-C3N4-NTs, (c) g-C3N4@RGO,(d) g-C3N4-NTs @RGO。
Fig. 4 is an ultraviolet-visible absorption spectrum of the prepared graphite-phase carbon nitride @ graphene provided by the embodiment of the present invention: (a) g-C3N4,(b) g-C3N4-NTs, (c) g-C3N4@RGO,(d) g-C3N4-NTs @RGO。
Fig. 5 is a graph showing the change of electrode potential with time before and after illumination when 304 stainless steel provided by the embodiment of the present invention is connected with a graphite-phase carbon nitride @ graphene photoanode in a 3.5% NaCl solution: (a) g-C3N4,(b) g-C3N4-NTs, (c) g-C3N4@RGO,(d) g-C3N4-NTs @ RGO. Wherein the abscissa is time(s) and the ordinate is electrode potential (V vs. AgCl/Ag). Light on means illumination and Light off means turning off the Light source, i.e. dark state.
Fig. 6 is a Mott-Schottky curve of the prepared graphite-phase carbon nitride @ graphene according to an embodiment of the present invention: (a) g-C3N4,(b) g-C3N4-NTs, (c) g-C3N4@RGO,(d) g-C3N4-NTs @RGO。
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of a graphite phase carbon nitride @ graphene composite film photoelectrode is provided, and the method is used for preparing g-C obtained by thermally decomposing melamine3N4Forming a dispersion liquid by the nanotube and graphene oxide according to a mass ratio of 1:1, and carrying out quenching treatment to obtain graphene oxide curled coating C3N4The preparation method comprises the following steps of (1) carrying out electrophoretic deposition on a nanotube, and carrying out thermal reduction at 350 ℃ to obtain a graphite-phase carbon nitride @ graphene composite film photoanode, wherein the preparation method specifically comprises the following steps:
(1) weighing 5g of melamine, grinding the melamine, putting the ground melamine into a corundum ark, putting the ark into an oscillator, and carrying out oscillation treatment at a medium speed for 10 min;
(2) moving the cover of the square boat into a tubular furnace, under the protection of nitrogen, heating to 500 ℃ at a speed of 10 ℃/min, calcining for 2h, then heating to 530 ℃ at a speed of 1 ℃/min, calcining for 2h, and naturally cooling to obtain the carbon nitride nanotube;
(3) weighing 0.1g of graphene oxide, dissolving in 100mL of deionized water, magnetically stirring for 20min, and then ultrasonically treating for 1h at 600W power to prepare a graphene oxide dispersion liquid;
(4) weighing 0.1g of carbon nitride nanotube, adding the graphene oxide dispersion liquid obtained in the step (3), and carrying out 400W power ultrasonic treatment for 1 h;
(5) transferring the dispersion liquid obtained in the step (4) into a plastic centrifuge tube, heating to 100 ℃, preserving heat for 10min, quickly placing the dispersion liquid into liquid nitrogen, and freeze-drying to obtain graphite-phase carbon nitride @ graphene oxide powder;
(6) and (3) adding 10mg of the composite powder obtained in the step (5) into 20mL of acetone, carrying out ultrasonic treatment for 10min, and weighing 5mg of iodine to be dissolved in the dispersion to form electrolyte. Applying a voltage of 20V for 10min by taking a platinum sheet as an anode and FTO conductive glass as a cathode, namely depositing composite powder on a conductive surface of the FTO, and naturally drying;
(7) and transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, heating to 350 ℃ at the speed of 2 ℃/min under the protection of argon, preserving the temperature for 1h, and naturally cooling to room temperature to obtain the graphite-phase carbon nitride @ graphene composite film photoanode.
Example 2
Graphite phase carbon nitride nanotube @ grapheneProcess for the preparation of a photoelectrode in which g-C obtained by thermal decomposition of melamine is used3N4Forming a dispersion liquid by the nanotube and graphene oxide according to a mass ratio of 1:2, and carrying out quenching treatment to obtain graphene oxide curled coating C3N4The preparation method comprises the following steps of (1) carrying out electrophoretic deposition on a nanotube, and carrying out thermal reduction at 350 ℃ to obtain a graphite-phase carbon nitride @ graphene composite film photoanode, wherein the preparation method specifically comprises the following steps:
(1) weighing 5g of melamine, grinding the melamine, putting the ground melamine into a corundum ark, putting the ark into an oscillator, and carrying out oscillation treatment at a medium speed for 10 min;
(2) moving the cover of the square boat into a tubular furnace, under the protection of nitrogen, heating to 500 ℃ at a speed of 10 ℃/min, calcining for 2h, then heating to 530 ℃ at a speed of 1 ℃/min, calcining for 2h, and naturally cooling to obtain the carbon nitride nanotube;
(3) weighing 0.1g of graphene oxide, dissolving in 100mL of deionized water, magnetically stirring for 20min, and then ultrasonically treating for 1h at 600W power to prepare a graphene oxide dispersion liquid;
(4) weighing 0.05g of carbon nitride nanotube, adding the graphene oxide dispersion liquid obtained in the step (3), and carrying out 400W power ultrasonic treatment for 1 h;
(5) transferring the dispersion liquid obtained in the step (4) into a plastic centrifuge tube, heating to 100 ℃, preserving heat for 10min, quickly placing the dispersion liquid into liquid nitrogen, and freeze-drying to obtain graphite-phase carbon nitride @ graphene oxide powder;
(6) and (3) adding 10mg of the composite powder obtained in the step (5) into 20mL of acetone, carrying out ultrasonic treatment for 10min, and weighing 5mg of iodine to be dissolved in the dispersion to form electrolyte. Applying a voltage of 20V for 10min by taking a platinum sheet as an anode and FTO conductive glass as a cathode, namely depositing composite powder on a conductive surface of the FTO, and naturally drying;
(7) and transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, heating to 350 ℃ at the speed of 2 ℃/min under the protection of argon, preserving the temperature for 1h, and naturally cooling to room temperature to obtain the graphite-phase carbon nitride @ graphene composite film photoanode.
Example 3
Preparation method of graphite-phase carbon nitride nanotube @ graphene photoelectrode, which comprises thermal decomposition ofPolycyanamine to obtain g-C3N4Dispersing the nanotube and graphene oxide in deionized water according to the mass ratio of 2:1, and performing quenching treatment to obtain graphene oxide curled coating C3N4The preparation method comprises the following steps of (1) carrying out electrophoretic deposition on a nanotube, and carrying out thermal reduction at 350 ℃ to obtain a graphite-phase carbon nitride @ graphene composite film photoanode, wherein the preparation method specifically comprises the following steps:
(1) weighing 5g of melamine, grinding the melamine, putting the ground melamine into a corundum ark, putting the ark into an oscillator, and carrying out oscillation treatment at a medium speed for 10 min;
(2) moving the cover of the square boat into a tubular furnace, under the protection of nitrogen, heating to 500 ℃ at a speed of 10 ℃/min, calcining for 2h, then heating to 530 ℃ at a speed of 1 ℃/min, calcining for 2h, and naturally cooling to obtain the carbon nitride nanotube;
(3) weighing 0.1g of graphene oxide, dissolving in 100mL of deionized water, magnetically stirring for 20min, and then ultrasonically treating for 1h at 600W power to prepare a graphene oxide dispersion liquid;
(4) weighing 0.2g of carbon nitride nanotube, adding the graphene oxide dispersion liquid obtained in the step (3), and carrying out 400W power ultrasonic treatment for 1 h;
(5) transferring the dispersion liquid obtained in the step (4) into a plastic centrifuge tube, heating to 100 ℃, preserving heat for 10min, quickly placing the dispersion liquid into liquid nitrogen, and freeze-drying to obtain graphite-phase carbon nitride @ graphene oxide powder;
(6) and (3) adding 10mg of the composite powder obtained in the step (5) into 20mL of acetone, carrying out ultrasonic treatment for 10min, and weighing 5mg of iodine to be dissolved in the dispersion to form electrolyte. Applying a voltage of 20V for 10min by taking a platinum sheet as an anode and FTO conductive glass as a cathode, namely depositing composite powder on a conductive surface of the FTO, and naturally drying;
(7) and transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, heating to 350 ℃ at the speed of 2 ℃/min under the protection of argon, preserving the temperature for 1h, and naturally cooling to room temperature to obtain the graphite-phase carbon nitride @ graphene composite film photoanode.
Example 4
A preparation method of a graphite-phase carbon nitride nanotube @ graphene photoelectrode is provided, and g-C is obtained by thermally decomposing melamine3N4Dispersing the nanotube and graphene oxide in deionized water according to the mass ratio of 2:1, and performing quenching treatment to obtain graphene oxide curled coating C3N4The preparation method comprises the following steps of (1) carrying out electrophoretic deposition on a nanotube, and carrying out thermal reduction at 400 ℃ to obtain a graphite-phase carbon nitride @ graphene composite film photoanode, wherein the preparation method specifically comprises the following steps:
(1) weighing 5g of melamine, grinding the melamine, putting the ground melamine into a corundum ark, putting the ark into an oscillator, and carrying out oscillation treatment at a medium speed for 10 min;
(2) moving the cover of the square boat into a tubular furnace, under the protection of nitrogen, heating to 500 ℃ at a speed of 10 ℃/min, calcining for 2h, then heating to 530 ℃ at a speed of 1 ℃/min, calcining for 2h, and naturally cooling to obtain the carbon nitride nanotube;
(3) weighing 0.1g of graphene oxide, dissolving in 100mL of deionized water, magnetically stirring for 20min, and then ultrasonically treating for 1h at 600W power to prepare a graphene oxide dispersion liquid;
(4) weighing 0.2g of carbon nitride nanotube, adding the graphene oxide dispersion liquid obtained in the step (3), and carrying out 400W power ultrasonic treatment for 1 h;
(5) transferring the dispersion liquid obtained in the step (4) into a plastic centrifuge tube, heating to 100 ℃, preserving heat for 10min, quickly placing the dispersion liquid into liquid nitrogen, and freeze-drying to obtain graphite-phase carbon nitride @ graphene oxide powder;
(6) and (3) adding 10mg of the composite powder obtained in the step (5) into 20mL of acetone, carrying out ultrasonic treatment for 10min, and weighing 5mg of iodine to be dissolved in the dispersion to form electrolyte. Applying a voltage of 20V for 10min by taking a platinum sheet as an anode and FTO conductive glass as a cathode, namely depositing composite powder on a conductive surface of the FTO, and naturally drying;
(7) and transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, heating to 400 ℃ at the speed of 2 ℃/min under the protection of argon, preserving the temperature for 1h, and naturally cooling to room temperature to obtain the graphite-phase carbon nitride @ graphene composite film photoanode.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The utility model provides a graphite phase carbon nitride @ graphene composite film photoanode for photoproduction cathodic protection which characterized in that: the graphite phase carbon nitride is a nanotube, and the graphene is a graphene roll.
2. The preparation method of the graphite-phase carbon nitride @ graphene composite film photoanode as claimed in claim 1, is characterized by comprising the following preparation steps:
(1) grinding melamine powder, placing the ground melamine powder into a corundum ark, carrying out medium-speed oscillation treatment for 5-20min, covering the corundum ark, moving the corundum ark into a tube furnace, heating the corundum ark to 500 ℃ at a speed of 10 ℃/min under a protective atmosphere, calcining the corundum ark for 1h, heating the corundum ark to 530 ℃ at a speed of 1 ℃/min, calcining the corundum ark for 1h, and naturally cooling the corundum ark to obtain a carbon nitride nanotube;
(2) sequentially adding graphene oxide powder and carbon nitride nanotubes into deionized water, and carrying out ultrasonic treatment for 1-2 h to uniformly mix; transferring the obtained dispersion liquid into a plastic centrifuge tube, heating for 10min, then quickly placing the dispersion liquid into liquid nitrogen, and carrying out freeze drying to obtain carbon nitride nanotube powder coated by graphene oxide;
(3) ultrasonically dispersing the carbon nitride nanotube coated by the graphene oxide obtained in the step (2) in acetone, and then adding a certain amount of iodine to obtain electrolyte; depositing the carbon nitride nanotube coated by the graphene oxide on the surface of the FTO conductive glass by adopting an electrophoretic deposition method and taking the FTO conductive glass as a negative electrode and a platinum sheet as a positive electrode, and naturally drying;
(4) transferring the FTO conductive glass into a corundum ark, transferring the corundum ark into a tube furnace, and roasting for 1h in a protective atmosphere to realize reduction of graphene oxide and obtain the carbon nitride nanotube @ graphene photoelectrode.
3. The method of claim 2, wherein: and (2) the protective atmosphere in the step (1) is nitrogen.
4. The method of claim 2, wherein: the graphene oxide in the step (2) is prepared by an improved Hummers method, the mass ratio of the carbon nitride nanotube to the graphene oxide is 1: 3-3: 1, the ultrasonic power is 400-800W, and the heating temperature is 60-100 ℃.
5. The method of claim 2, wherein: the concentration of the carbon nitride nanotube powder coated in the electrolyte in the step (3) is 0.1-0.5 g/L, the mass ratio of the powder to iodine is 1: 1-3: 1, the electrophoretic deposition voltage is 15-30V, and the deposition time is 5-20 min.
6. The method of claim 2, wherein: in the step (4), the protective atmosphere is argon, the roasting temperature is 300-450 ℃, and the heating rate is 1-5 ℃/min.
7. The application of the graphite-phase carbon nitride @ graphene composite film photoanode in the field of photoproduction cathode protection in claim 1.
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| CN113791129A (en) * | 2021-08-23 | 2021-12-14 | 广州大学 | Copper ion electrochemiluminescence detection electrode, detector, preparation method and application thereof |
| CN115155636A (en) * | 2022-06-28 | 2022-10-11 | 浙江大学 | Sodium-boron-codoped carbon nitride photocatalyst, reduced graphene oxide composite membrane, and preparation method and application of composite membrane |
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