CN113231095A - Carbon nitride heterojunction photocatalyst and preparation method and application thereof - Google Patents
Carbon nitride heterojunction photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/54—Acetic acid
Abstract
The invention discloses a carbon nitride heterojunction photocatalyst and application thereof.A heterostructure is formed by utilizing metal oxide and carbon nitride, so that the separating capacity of electrons and holes is improved, the absorption of visible light by the heterostructure is improved, graphene is further doped, the transmission of electrons and the dispersity of the catalyst are improved, and the photocatalytic effect is better improved. The invention also discloses the application of the carbon nitride heterojunction photocatalytic electrode in the production of acetic acid by reducing carbon dioxide in a microbial electrosynthesis system, on one hand, under the carbon nitride heterojunction photocatalytic electrode, the rate of electrons obtained from a cathode is improved by the combination of photoproduction electrons and holes, which are used for combining with electrons transmitted from an anode, and the photoproduction electrons can be further transmitted to autotrophic microorganisms, and finally, the purpose of improving the efficiency of reducing the carbon dioxide in the bioelectrochemistry synthesis system to produce the acetic acid is achieved by providing additional electron supply and driving force.
Description
Technical Field
The invention relates to a microbial electrosynthesis technology, in particular to a carbon nitride heterojunction photocatalyst and a preparation method and application thereof.
Background
The global economic growth and industrialization bring about rapid growth of energy demand, so that the use of energy fuels is further increased, and the conventional fossil fuels are combusted, a large amount of carbon dioxide is discharged into the atmosphere, so that climate change is further caused, a greenhouse effect is generated, and the like, so that the carbon emission is reduced, the carbon neutralization is realized, the method is an important measure for coping with climate change and realizing human sustainable development, and the carbon capture, utilization and sequestration are one of important strategic technologies for solving the low-carbonization development of the coal-based energy system in China, and are currently researched hot spots.
Microbial Electrosynthesis (MES) is a bioelectrochemical technology developed in recent years, which integrates technologies and means in many related fields such as environmental technology, microbiology, electrochemistry, material science, engineering and analytical chemistry. Microbial electrosynthesis occurs in a bioelectrochemical system comprising a cathode, an anode, separated by an ion exchange membrane, and immersed in an electrolyte solution. At the anode H2Oxidation of O to produce O2、H+And electrons are transferred from the anode to the cathode through an external circuit, and H + permeates into the cathode chamber through the ion exchange membrane. The biocatalyst on the cathode utilizes the electrons and protons obtained to convert the CO2Reducing to organic compounds with more carbon, applying a certain voltage/potential across the electrodes to ensure biological reduction of CO2The reaction of (3) proceeds. The microbial electrosynthesis can directly produce the required organic chemicals through microorganisms and secrete the organic chemicals to the outside of cells, the further processing of biomass is not needed for product production, the energy consumption and the waste water in the biomass treatment process are reduced, and the influence on the environment in the biomass degradation treatment process is avoided.
From the perspective of an electron transfer path, the activity of a microbial catalyst in a microbial electrosynthesis system is influenced by the physical and chemical properties of an electrode material, so that the electron transfer rate between an electrode and a microbe is changed, and finally, the efficiency of the microbial electrosynthesis of chemicals is greatly influenced. For example, the carbon cloth electrode is modified by chitosan rich in amino and hydroxyl, so that the yield of acetic acid is improved by 7.6 times; the carbon nano tube is modified on the foam carbon electrode, the specific surface area and the conductivity of the electrode are considered, and the yield of the acetic acid is improved by more than 2.6 times. In addition, the carbon-based electrode can be modified by graphene oxide to enhance the conductivity of the electrode and increase the rate of acetic acid production by MES. From the present, a great deal of strategies focus on improving the specific surface area of the electrode, enhancing the conductivity of the electrode, improving the biocompatibility and enhancing the hydrogen evolution performance of the electrode so as to improve the efficiency of MES chemical production, while neglecting to provide additional reducing power for the catalysis of carbon dioxide by the autotrophic microorganisms by increasing additional electron supply.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problem of slow electron transfer rate in the conventional microbial electrosynthesis, the invention provides a preparation method of a carbon nitride heterojunction photocatalyst electrode and application of the carbon nitride heterojunction photocatalyst electrode in a microbial electrosynthesis system.
In order to achieve the above object, the present invention provides a carbon nitride heterojunction photocatalyst, which is prepared by the following method:
(1) dissolving graphene oxide in distilled water, performing ultrasonic treatment, and adjusting the pH to 9-11;
(2) adding a metal oxide into the graphene oxide solution obtained in the step (1), and carrying out ultrasonic treatment for 2-4 h;
(3) adding a certain amount of carbon nitride into the graphene oxide solution containing the metal oxide, stirring for 12-16h, reacting the final mixture in a reaction kettle (normal pressure) at a certain temperature, and then freeze-drying to obtain the carbon nitride heterojunction catalyst, wherein preferably, the freeze-drying condition is-20 ℃ for 24 h.
The carbon nitride can be prepared by the methods disclosed in the prior art, such as the preparation of carbon nitride by using melamine. Specifically, melamine is placed in a crucible and heated to 550 ℃ in a muffle furnace, and the temperature is kept for 2-4 h; cooling to room temperature, performing ultrasonic treatment in 0.1M nitric acid solution for 8-10h, washing with deionized water to neutrality, and drying at 60-80 deg.C to obtain carbon nitride.
Wherein, the metal oxide is copper oxide, zinc oxide, tungsten oxide and tin oxide.
The mass ratio of the carbon nitride to the metal oxide to the graphene is 1:1:0.2-2, preferably 1:1: 0.4.
In the step (3), the reaction temperature is 160-220 ℃, and the reaction time is 20-24 h. Preferably, the reaction temperature is 180 ℃ and the reaction time is 22 h.
The invention further provides the application of the carbon nitride heterojunction photocatalyst in preparing the photocatalytic electrode, the carbon nitride heterojunction catalyst is dissolved in a solvent to prepare a catalyst solution, the pretreated electrode is immersed in the catalyst solution, and is taken out after being stirred for 6-10h and dried to obtain the photocatalytic electrode.
Wherein the solvent is obtained by mixing 1-3 wt% of perfluorosulfonic acid polymer aqueous solution and 80-95% of ethanol aqueous solution by volume concentration, and the volume ratio of the two is 1-5: 10. Preferably, the volume ratio of the two is 1: 5.
The electrode is any one of carbon felt, carbon paper or carbon cloth.
Preferably, the electrode is pretreated by 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking in sodium hydroxide for 6h, cleaning to neutrality and drying.
The loading amount of the carbon nitride heterojunction catalyst is 5-40mg cm relative to the surface area of the electrode-2Preferably 20mg
-2
cm。
The invention further provides application of the photocatalytic electrode in production of acetic acid by reducing carbon dioxide in a microbial electrosynthesis system.
Specifically, in the microbial electrosynthesis system, a carbon felt, a carbon cloth or a carbon paper is taken as an anode, the carbon nitride heterojunction photocatalytic electrode is taken as a cathode, a proton exchange membrane divides the microbial electrosynthesis system into a cathode chamber and an anode chamber, autotrophic microorganisms are inoculated into the cathode chamber, a potential of-0.8V to-1.2V vs Ag/AgCl and an iodine tungsten lamp are added, and a 100W iodine tungsten lamp is preferably added, so that the light source intensity is 20-50mW m mW-2And introducing carbon dioxide gas to carry out electrocatalytic reduction on the carbon dioxide to produce the acetic acid.
Preferably, the autotrophic microorganisms are obtained by long-term enrichment acclimatization of activated sludge in hydrogen and carbon dioxide atmosphere, and the preparation method is shown in (J Chem Technol Biotechnol 2018; 93: 457-466). The anolyte in the anode chamber comprises the following components: 6g/L of NaCl, 2g/L of KCl and water as a solvent; in the cathode chamberThe composition of the catholyte is as follows: NH (NH)4Cl 0.5g/L，KCl 0.1g/L，MgSO4·7H2O 0.1g/L，NaCl 0.5g/L，KH2PO4 0.1g/L，CaCl20.01 g/L，NaHCO30.5g/L and the solvent is water.
Has the advantages that: according to the invention, a heterostructure is formed by utilizing the metal oxide and the carbon nitride, so that the separation capability of electrons and holes is improved, the absorption of the heterostructure on visible light is improved, the graphene is further doped, the transmission of electrons and the dispersity of a catalyst are improved, and the photocatalysis effect is better improved; under the carbon nitride heterojunction photocatalytic electrode, on one hand, the hole is used for being combined with the electron transmitted from the anode through the photo-generated electron and the hole, so that the driving force is obtained to improve the speed of obtaining the electron from the cathode, the photo-generated electron can be further transmitted to autotrophic microorganisms, and finally, the purpose of improving the acetic acid production efficiency of reducing carbon dioxide by the bioelectricity synthesis system is achieved by providing extra electron supply and driving force.
Drawings
Figure 1XRD pattern of carbon nitride;
fig. 2 SEM image of copper oxide-carbon nitride-graphene loaded on the electrode;
FIG. 3 is a photoluminescence spectrum of different catalysts;
FIG. 4 is a linear scan of different catalysts.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which will be helpful for understanding the present invention, but the scope of the present invention is not limited to the examples.
Example 1
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; after cooling to room temperature, the mixture is treated by ultrasonic treatment in 0.1M nitric acid solution for 8 hours, finally washed to be neutral by deionized water and dried at 60 ℃. It can be seen from XRD in FIG. 1 that carbon nitride is obtained after melamine is decomposed at high temperature and dried. Dissolving graphene oxide in distilled water, performing ultrasonic treatment for 30 minutes, and adjusting the pH to 9 by using NaOH to obtain a graphene oxide solution. Adding copper oxide into graphene oxide solution for ultra-high temperature annealingAnd (3) sounding for 2h, adding carbon nitride into the graphene oxide solution containing the metal oxide in a mass ratio of 1:1:0.8, stirring for 12h, and reacting the final mixture in a reaction kettle at 180 ℃ for 12 h. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 10. The carbon felt is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking the carbon felt in sodium hydroxide for 6h, cleaning the carbon felt to be neutral and drying the carbon felt, adding the pretreated carbon felt into a catalyst solution, stirring the solution for 8h, taking the solution out, and finally, the catalyst is loaded on an electrode as can be seen from an electron microscope image in figure 2, wherein the content of the catalyst is 15mg cm-2。
The copper oxide-carbon nitride-graphene photocatalyst electrode prepared in the embodiment is used as a cathode, and the copper oxide electrode, the carbon nitride electrode and the graphene electrode with the same loading and preparation processes are used as a cathode contrast. The cathode chamber was inoculated with an electro-autotrophic microorganism (see (J Chem Technol Biotechnol 2018; 93: 457-466)) and a potential of-1.05V vs Ag/AgCl was applied between the cathode and the anode with a light source intensity of 30mW m-2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.4g L-1. The final concentration is the highest copper oxide-carbon nitride-graphene photocatalyst electrode, and the concentration of acetic acid can reach 5.6g L-1And secondly a graphene electrode (4.6g L)-1) And copper oxide (4.5g L)-1) Electrode, carbon nitride electrode 4.0g L-1The blank carbon felt is the lowest (2.8g L)-1). Under the same condition, the concentration of acetic acid of the copper oxide-carbon nitride-graphene photocatalyst without illumination is 3.3g L at most-1. This shows that the copper oxide-carbon nitride-graphene photocatalyst can effectively provide additional electrons and driving force through photocatalysis to improve the performance of microbial electrosynthesis.
Fig. 3 is a photoluminescence spectrum (PL) test of various photocatalytic electrodes prepared in this example, and the peak intensity of the copper oxide-carbon nitride-graphene photocatalyst electrode is the lowest compared with the other two photocatalysts, which shows that the recombination rate of photogenerated hole-electron pair is slow, so that the electron and the hole can be more easily separated and used in a microbial electrosynthesis system.
Fig. 4 is a linear scan of various electrodes prepared in this example, where the greater the current response of the electrode, the higher the electrocatalytic activity, over the linear scan range. As can be seen from fig. 4, the current response of the blank carbon felt is minimum, the carbon nitride, copper oxide and graphene electrodes are all better than the blank carbon felt, and the catalytic activity of the copper oxide-carbon nitride-graphene photocatalyst electrode is the highest and higher than that of the copper oxide-carbon nitride-graphene photocatalyst electrode alone, which indicates that the co-doping of the copper oxide-carbon nitride-graphene can better improve the photoelectrocatalysis, so as to improve the yield of the microbial electrosynthesis system for reducing carbon dioxide to synthesize acetic acid.
Example 2
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; and cooling to room temperature, carrying out ultrasonic treatment in a 0.1M nitric acid solution for 8 hours, finally washing to be neutral by deionized water, and drying at 60 ℃ to obtain the carbon nitride. Graphene oxide was dissolved in distilled water, sonicated for 30 minutes, and then pH adjusted to 9 with NaOH. And adding zinc oxide into the obtained graphene oxide solution, and carrying out ultrasonic treatment for 3 h. Adding carbon nitride into the graphene oxide solution containing the metal oxide in a mass ratio of 1:1:0.4, stirring for 12 hours, and reacting the final mixture in a reaction kettle at 180 ℃ for 22 hours. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 5. The carbon felt is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking the carbon felt in sodium hydroxide for 6h, cleaning the carbon felt to be neutral and drying the carbon felt, adding the pretreated carbon felt into a catalyst solution, stirring the mixture for 8h, and taking the mixture out, wherein the final catalyst content is 20mg cm-2。
The carbon felt is used as an anode, the carbon nitride heterojunction photocatalytic electrode prepared in the embodiment is used as a cathode, the cathode chamber is inoculated with the electro-autotrophic microorganisms (the preparation method is shown in J Chem Technol Biotechnol 2018; 93: 457--2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.8g L-1。
Example 3
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; and cooling to room temperature, carrying out ultrasonic treatment in a 0.1M nitric acid solution for 8 hours, finally washing to be neutral by deionized water, and drying at 60 ℃ to obtain the carbon nitride. Graphene oxide was dissolved in distilled water, sonicated for 30 minutes, and then pH adjusted to 9 with NaOH. And adding copper oxide into the obtained graphene oxide solution, and carrying out ultrasonic treatment for 4 h. Adding carbon nitride into the graphene oxide solution containing the metal oxide in a mass ratio of 1:1:0.2, stirring for 12 hours, and reacting the final mixture in a reaction kettle at 160 ℃ for 20 hours. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 10. The carbon felt is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking the carbon felt in sodium hydroxide for 6h, cleaning the carbon felt to be neutral and drying the carbon felt, adding the pretreated carbon felt into a catalyst solution, stirring the mixture for 8h, and taking the mixture out, wherein the final catalyst content is 10mg cm-2。
The carbon felt is used as an anode, the carbon nitride heterojunction photocatalytic electrode prepared in the embodiment is used as a cathode, the cathode chamber is inoculated with the electro-autotrophic microorganisms (the preparation method is shown in J Chem Technol Biotechnol 2018; 93: 457--2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.4g L-1。
Example 4
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; and cooling to room temperature, carrying out ultrasonic treatment in a 0.1M nitric acid solution for 8 hours, finally washing to be neutral by deionized water, and drying at 60 ℃ to obtain the carbon nitride. Graphene oxide was dissolved in distilled water, sonicated for 30 minutes, and then pH adjusted to 9 with NaOH. And adding copper oxide into the obtained graphene oxide solution, and carrying out ultrasonic treatment for 2 h. Adding carbon nitride to the above-mentioned metal-containing oxideAnd (3) adding the mixture into a graphene oxide solution in a mass ratio of 1:1:2, stirring for 12 hours, and reacting the final mixture in a reaction kettle at 160 ℃ for 12 hours. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 8. The carbon felt is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking the carbon felt in sodium hydroxide for 6h, cleaning the carbon felt to be neutral and drying the carbon felt, adding the pretreated carbon felt into a catalyst solution, stirring the solution for 8h, and taking the carbon felt out, wherein the final catalyst content is 15mg cm-2。
The carbon felt is used as an anode, the carbon nitride heterojunction photocatalytic electrode prepared in the embodiment is used as a cathode, the cathode chamber is inoculated with the electro-autotrophic microorganisms (the preparation method is shown in J Chem Technol Biotechnol 2018; 93: 457--2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.4g L-1。
Example 5
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; and cooling to room temperature, carrying out ultrasonic treatment in a 0.1M nitric acid solution for 8 hours, finally washing to be neutral by deionized water, and drying at 60 ℃ to obtain the carbon nitride. Graphene oxide was dissolved in distilled water, sonicated for 30 minutes, and then pH adjusted to 9 with NaOH. And adding tungsten oxide into the obtained graphene oxide solution, and carrying out ultrasonic treatment for 4 h. Adding carbon nitride into the graphene oxide solution containing the metal oxide in a mass ratio of 1:1:1, stirring for 12 hours, and reacting the final mixture in a reaction kettle at 160 ℃ for 18 hours. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 10. The carbon cloth is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking in sodium hydroxide for 6h, cleaning to neutral, oven drying, adding the pretreated carbon cloth into catalyst solution, stirring for 8h, and taking out to obtain final catalyst with content of 15mg cm-2。
The carbon cloth is used as an anode, the carbon nitride heterojunction photocatalytic electrode prepared in the embodiment is used as a cathode, the cathode chamber is inoculated with the electro-autotrophic microorganisms (the preparation method is shown in J Chem Technol Biotechnol 2018; 93: 457--2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.5g L-1。
Example 6
Putting melamine into a crucible, heating the crucible to 550 ℃ in a muffle furnace, and keeping the temperature for 4 hours; and cooling to room temperature, carrying out ultrasonic treatment in a 0.1M nitric acid solution for 8 hours, finally washing to be neutral by deionized water, and drying at 60 ℃ to obtain the carbon nitride. Graphene oxide was dissolved in distilled water, sonicated for 30 minutes, and then pH adjusted to 9 with NaOH. And adding tin oxide into the obtained graphene oxide solution, and carrying out ultrasonic treatment for 4 h. Adding carbon nitride into the graphene oxide solution containing the metal oxide in a mass ratio of 1:1:0.5, stirring for 12 hours, and reacting the final mixture in a reaction kettle at 160 ℃ for 16 hours. And then freeze-drying for 24h at the temperature of minus 20 ℃ to obtain the carbon nitride heterojunction catalyst. The catalyst was then dissolved in a mixture of 5% Nafion solution and 95% aqueous ethanol at a volume ratio of 1: 10. The carbon paper is used in advance with 1mol L-1Soaking in hydrochloric acid for 6h, cleaning to neutral, oven drying, and adding 1mol L-1Soaking in sodium hydroxide for 6h, cleaning to neutral, oven drying, adding the pretreated carbon paper into catalyst solution, stirring for 8h, and taking out to obtain final catalyst with content of 30mg cm-2。
The carbon felt is used as an anode, the carbon nitride heterojunction photocatalytic electrode prepared in the embodiment is used as a cathode, the cathode chamber is inoculated with the electro-autotrophic microorganisms (the preparation method is shown in J Chem Technol Biotechnol 2018; 93: 457--2The reaction is carried out for 30 days under the condition of introducing 100 percent of carbon dioxide, and the final acetic acid concentration reaches 5.6g L-1。
The present invention provides a concept and a method of a carbon nitride heterojunction photocatalyst, and a method and a way for implementing the technical scheme are many, the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of 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. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A carbon nitride heterojunction photocatalyst is characterized by being prepared by the following method:
(1) dissolving graphene oxide in distilled water, performing ultrasonic treatment, and then adjusting the pH value to 9-11 to obtain a graphene oxide solution;
(2) adding a metal oxide into the graphene oxide solution obtained in the step (1), and performing ultrasonic treatment for 2-4h to obtain a graphene oxide solution containing the metal oxide;
(3) adding a certain amount of carbon nitride into the graphene oxide solution containing the metal oxide, stirring for 12-16h, finally reacting the mixture in a reaction kettle at a certain temperature, and then freeze-drying to obtain the carbon nitride heterojunction catalyst.
2. A carbon nitride heterojunction photocatalyst as claimed in claim 1, wherein said metal oxide is copper oxide, zinc oxide, tungsten oxide and tin oxide.
3. The carbon nitride heterojunction photocatalyst according to claim 1, wherein the mass ratio of the carbon nitride to the metal oxide to the graphene is 1:1: 0.2-2.
4. The carbon nitride heterojunction photocatalyst as claimed in claim 1, wherein in the step (3), the reaction temperature is 160-220 ℃ and the reaction time is 20-24 h.
5. The use of a carbon nitride heterojunction photocatalyst as claimed in any of claims 1 to 4 in the preparation of a photocatalytic electrode, wherein the carbon nitride heterojunction catalyst is dissolved in a solvent to prepare a catalyst solution, the pretreated electrode is immersed in the catalyst solution, stirred for 6 to 10 hours and then removed and dried to obtain the photocatalytic electrode.
6. The use according to claim 5, wherein the solvent is obtained by mixing 1-3 wt% of an aqueous solution of a perfluorosulfonic acid-type polymer with 80-95 vol% of an aqueous solution of ethanol, the volume ratio of which is 1-5: 10.
7. Use according to claim 5, wherein the electrode is a carbon felt, a carbon cloth or a carbon paper.
8. Use according to claim 5, wherein the carbon nitride heterojunction catalyst is supported at a loading of 5-40mg cm relative to the surface area of the electrode-2。
9. Use of the photocatalytic electrode prepared according to claim 5 in the production of acetic acid by reduction of carbon dioxide in a microbial electrosynthesis system.
10. The use according to claim 8, wherein in the microbial electrosynthesis system, a carbon felt, a carbon cloth or a carbon paper is used as an anode, the carbon nitride heterojunction photocatalytic electrode is used as a cathode, a proton exchange membrane divides the microbial electrosynthesis system into a cathode chamber and an anode chamber, the cathode chamber is inoculated with autotrophic microorganisms, and a potential of-0.8V to-1.2V vs Ag/AgCl and a iodine tungsten lamp are added, so that the intensity of a light source is 20-50mW m-2And introducing carbon dioxide gas to carry out electrocatalytic reduction on the carbon dioxide to produce the acetic acid.
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