CN114471655B - Preparation method of composite photocatalyst capable of efficiently generating hydrogen peroxide without adding sacrificial agent under visible light - Google Patents

Preparation method of composite photocatalyst capable of efficiently generating hydrogen peroxide without adding sacrificial agent under visible light Download PDF

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CN114471655B
CN114471655B CN202210040454.6A CN202210040454A CN114471655B CN 114471655 B CN114471655 B CN 114471655B CN 202210040454 A CN202210040454 A CN 202210040454A CN 114471655 B CN114471655 B CN 114471655B
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hydrogen peroxide
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visible light
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CN114471655A (en
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石建惠
曾剑
李英
罗一飞
高龙胜
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Shanxi Ecological Environment Protection Service Center Shanxi Environmental Planning Institute
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Abstract

The photocatalytic production of hydrogen peroxide from g-C 3N4 using water and oxygen is a very promising and sustainable process. However, the yield of pure g-C 3N4 to H 2O2 is not ideal due to limited light absorption, rapid photogenerated electron-hole recombination and poor surface electron transport. Therefore, the porous g-C 3N4 is modified by doping phosphorus and loaded carbon quantum dots by adopting a high-temperature calcination and hydrothermal method to synthesize the P-P 1CN/CQDs25 composite photocatalyst. Phosphorus serves as a bridge for electron transfer, induces electrons into CQDs, which serve as electron capturing materials, capturing and stabilizing photogenerated electrons. Since CQDs have unique optical properties, light absorption can also be enhanced. Under the condition of no addition of a sacrificial agent and oxygen ventilation, the P-P 1CN/CQDs25 shows high-rise H 2O2 generation activity, the generation amount of H 2O2 after reaction 5H reaches 494 mu M/L, and the generation rate constant K f is 238 mu M H ‑1.

Description

Preparation method of composite photocatalyst capable of efficiently generating hydrogen peroxide without adding sacrificial agent under visible light
Technical Field
The invention relates to a preparation technology of a photocatalyst, in particular to a preparation method of a composite photocatalyst capable of efficiently generating hydrogen peroxide without adding a sacrificial agent under visible light.
Background
With the increasing concern of human society for environmental pollution and new energy sources, hydrogen peroxide (H 2O2) is considered as an important green oxidant and promising future fuel as an ideal resource for solving environmental problems and energy crisis [1-3]. H 2O2 has even higher energy density than compressed H 2 gas, and is expected to replace traditional fossil fuels in the future [3, 4-6]. However, the current generation of large-scale H 2O2 still depends on the traditional anthraquinone-based method, and the traditional method has the defects of complex process, high energy consumption, high organic solvent input, toxic byproducts, explosion hazard and the like [7-9]. Currently, electrocatalytic and photocatalytic production of H 2O2 has attracted considerable interest to many researchers as an emerging alternative to traditional methods [10-13]. In contrast to the severe energy consumption of the electrocatalytic process, the photocatalytic process is an energy-efficient, environmentally friendly and sustainable process that captures sunlight under mild conditions and drives a semiconductor catalyst to produce H 2O2 [14-16].
Generally, the mechanism of photocatalytic H 2O2 is mainly generated by reduction reaction of electrons in the appropriate conduction band with oxygen under light. The generation route is mainly through direct double electron reaction (formula 1) [17-20] or continuous two-step single electron reaction (formulas 2 and 3) [21-23] taking superoxide radical (O 2 -) as intermediate. Based on the above generation process, the photocatalytic generation of H 2O2 is mainly determined by good light absorption, proper conduction band position, ideal photogenerated carrier separation and surface electron transfer, a certain adsorbed oxygen concentration on the photocatalyst surface, and the like.
In recent years, graphite-phase carbon nitride (g-C 3N4) has become an ideal candidate for photocatalytic generation of H 2O2 as an emerging class of metal-free polymer photocatalysts based on their stable physicochemical properties, suitable energy band structure, ease of preparation, non-toxicity and low cost advantages [24-27]. Notably, its superior conduction band position (about-1.3 eV) can catalyze all reactions in equations 1-3 [28]. However, the yield of photocatalytic H 2O2 produced by bulk g-C 3N4 is still far from satisfactory [29-32]. In order to improve the efficiency of the photocatalytic production of H 2O2, some key problems in the process of g-C 3N4 photocatalytic production of H 2O2 need to be solved: limited light absorption, fast photo-generated electron-hole recombination, and poor surface electron transport. Because these problems can cause the photogenerated electrons to recombine with holes or deactivate before reacting with oxygen.
To overcome the above problems, researchers have proposed various methods to modify pure g-C 3N4, including constructing heterojunction and Z-system （g-C3N4-CoWO,AgBr-Br/g-C3N4,CuO/g-C3N4,Cu2（OH）2CO3/g-C3N4,Ni-CAT/g-C3N4,Bi4O5Br2/g-C3N4）[17, 20, 33-36] or introducing defects [26, 31, 37-40] to expand the light absorption range and improve the separation of photogenerated electron holes; or by supporting noble metal (Au/g-C 3N4) [41], monoatomic (Co 1/g-C3N4) [42] or carbon material (g-C 3N4 -CNTs) [43] to accelerate the surface mobility of the photogenerated electrons. However, if the separated and migrated photogenerated electrons and holes are not trapped and immobilized, they still have a great opportunity to recombine, thereby reducing the chance of the photogenerated electrons reacting with oxygen. So researchers have also added sacrificial agents as hole-trapping agents to inhibit photo-generated electron-hole recombination, while continuing to introduce oxygen to increase oxygen diffusion at the photocatalyst surface, promoting electron-oxygen reactions [44]. However, adding the sacrificial agent and bubbling oxygen adds cost and requires an additional process to remove the by-products of the sacrificial agent [45].
Reference is made to:
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Disclosure of Invention
The invention provides a preparation method of a composite photocatalyst for efficiently generating hydrogen peroxide without adding a sacrificial agent under visible light, which aims to solve the technical problems of limited light absorption, rapid photo-generated electron-hole recombination and poor surface electron migration existing in the conventional g-C 3N4 photocatalytic generation of H 2O2, and further low H 2O2 yield.
The invention is realized by adopting the following technical scheme: a preparation method of a composite photocatalyst capable of efficiently generating hydrogen peroxide without adding a sacrificial agent under visible light comprises the following steps:
1) Synthesis of phosphorus doped porous g-C 3N4
The porous g-C 3N4 doped with phosphorus is synthesized by adopting a thermal polymerization method: evenly mixing melamine hydrochloride and hexachloromelamine, wherein the mass ratio of the melamine hydrochloride to the hexachloromelamine is 10: x, wherein x is 0.5-1.5; placing the mixture in a crucible with a cover, calcining the mixture for 3-5 hours at a heating speed of 3-10 ℃/min at 530-560 ℃ by utilizing a muffle furnace, wherein the obtained yellow powder is porous g-C 3N4 doped with phosphorus, which is called P-P x CN for short, and x represents the addition amount of hexachloromelamine;
2) Synthesis of carbon quantum dots
Preparing carbon quantum dots by an alkali-assisted ultrasonic method: uniformly dissolving glucose in deionized water, adding ammonia water with the concentration of 1mol/L, carrying out ultrasonic treatment for 1.5-3 hours, and continuously stirring for 6-9 hours, wherein the concentration ratio of the glucose solution to the ammonia water is 0.5-1.5:1, and the volume ratio of the glucose solution to the ammonia water is 2:1-1:2; adding hydrochloric acid to adjust the pH value of the mixed solution to be 7, dialyzing through an MWCO 3000 semipermeable membrane to finally obtain a transparent brown solution, namely CQDs aqueous solution, and storing the transparent brown solution in a refrigerator at 4 ℃ for later use;
3) Synthesis of composite photocatalyst P-P xCN/CQDsy
CQDs are supported on P-P x CN by hydrothermal method: adding P-P x CN and CQDs solution into 30-80 ml deionized water, wherein the proportion relation is that 20-30 ml CQDs solution is added into each gram of P-P x CN, stirring for 4-10 hours at room temperature, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave, and reacting for 6-9 hours at 170-190 ℃, wherein the obtained sample is simply referred to as P-P xCN/CQDsy, and y is the addition amount of the CQDs solution.
The present invention contemplates the introduction of an electron capturing material to capture and immobilize the photo-generated electrons, thereby increasing the reaction opportunity between the electrons and oxygen and improving the yield of photocatalytic production of H 2O2. While also addressing how photogenerated electrons can be induced into the electron trapping material.
To achieve the above idea, the inventors designed to synthesize a P-P 1CN/CQDs25 composite photocatalyst by doping phosphorus (P) and supported Carbon Quantum Dots (CQDs) to modify porous g-C 3N4 (P-CN) using a high temperature calcination and hydrothermal method. On one hand, the doped P is used as a bridge for electron transfer, and the photo-generated electrons are induced to enter CQDs so as to promote the separation of photo-generated electron holes; on the other hand, it can also increase the adsorption of oxygen and promote the reduction reaction between photo-generated electrons and the adsorbed oxygen. And for CQDs, because of the unique property of capturing, transferring and storing electrons, the CQDs are selected as electron capturing materials to further enhance the separation of photo-generated electron holes, stabilize photo-generated electrons and accelerate the efficient reaction of electrons and oxygen. At the same time, CQDs also have unique optical properties that can improve the light absorption capacity of the composite and widen the light response range. In summary, doped P and supported CQDs can optimize optical absorption, photogenerated electron-hole separation, surface electron transport, and electron to oxygen reduction simultaneously. In the step 2, the use of ammonia water alkali liquor in an alkali-assisted ultrasonic method can prepare CQDs with better crystalline phase, the lattice fringes are 0.34nm, and the loading of the CQDs can better promote the photocatalytic H 2O2, production of the compound, and the result is shown in figure 6. And step 3, compounding the P-P x CN and the CQD by a hydrothermal method to obtain a compound photocatalytic material P-P xCN/CQDsy which is tightly connected with the P-P x CN and the CQD, as shown in figures 2c and d.
Further, in the step (1), x is 1; and (3) taking the values of y as 20ml, 25ml and 30ml in the step (3) to finally obtain P-P 1CN/CQDs20、p-P1CN/CQDs25 and P-P 1CN/CQDs30.
The P-P 1CN/CQDs25 composite photocatalyst can obtain high H 2O2 yield under the conditions of no addition of a sacrificial agent and no oxygen exposure under the visible light. With the H 2O2 yield up to 494. Mu.M/L (21 and 14 times P-CN and P-P 1 CN, respectively) after reaction 5H, the rate constant K f was 238. Mu. M H-1 (34 and 22 times P-CN and P-P 1 CN, respectively). The invention provides a new idea for designing a novel photocatalyst for efficiently generating H 2O2.
The invention has the beneficial effects that: 1. the composite photocatalyst P-P xCN/CQDsy designed and synthesized by the invention, wherein doped P is used as a bridge for electron transfer to induce electrons to enter CQDs, and meanwhile, the CQDs are used as electron capturing materials to capture and stabilize photo-generated electrons. In addition, since CQDs have unique optical characteristics, light absorption can be enhanced. Thus, the doped phosphorus and the supported carbon sites can solve the proposed problems simultaneously: limited light absorption, fast photogenerated electron-hole recombination and poor surface electron transport. The idea is ingenious and novel, and related researches are rarely reported at present.
2. P-P xCN/CQDsy (exemplified by x=1, y=25) exhibited highly enhanced H 2O2 production activity under visible light without the addition of a sacrificial agent and oxygen passage, up to 494 μm/L of H 2O2 production (21 and 14 times P-CN and P-P 1 CN, respectively) after reaction 5H, and 238 μ M H-1 (34 and 22 times P-CN and P-P 1 CN, respectively) production rate constant K f.
Drawings
XRD pattern of the sample of fig. 1.
TEM image of the sample of FIG. 2 (a) P-CN, (b) P-P 1CN,（c）p-P1CN/CQDs25,（d）,p-CN/CQDs25, an enlarged view of the circled portion in (c).
Results of uv-visible absorption and band structure of the samples of fig. 3 (a) uv-visible absorption, (b) mott-schottky curve, (c) XPS valence band spectrum, (d) and (e) theoretical calculated DOS plot of P-P 1 CN and P-P 1CN/CQDs25, (f) presumed band structure of the samples.
The electrochemical test results for the sample of fig. 4 are shown in (a) a fluorescence test PL, (b) an electrochemical impedance test EIS, (c) a transient photocurrent result without fast electron scavenger (MVCl 2), and (d) a transient photocurrent result with fast electron scavenger (MVCl 2).
The results of photocatalytic H 2O2 for the samples of fig. 5 (without sacrificial agent and without oxygen exposure) (a) results for H 2O2 production by the samples under visible light (b) results for H 2O2 production by the samples under near infrared light (c) results for H 2O2 decomposition by the samples (initial H2O2 concentration of 1.25 mmol L −1), (d) rate constants for H 2O2 production by the samples under visible light and rate constants for decomposition.
Fig. 6: the results of the hydrogen peroxide production of the p-CN/CQDs 25 composites loaded with different CQDs, (A) CQDs prepared by using ammonia water (1 mol/L) in an alkaline solution ultrasonic method; (B) CQDs are prepared using sodium hydroxide (1 mol/L) in an alkaline solution sonication process.
Detailed Description
For comparison with the case of no phosphorus doping, a phosphorus-free porous g-C 3N4 (p-CN) and a phosphorus-doped porous g-C 3N4（p-Px CN were synthesized, respectively, as follows.
1. Synthesis of porous g-C 3N4 (p-CN)
Porous g-C 3N4 was prepared by a thermal polymerization process. Specifically, 15g melamine was added to 150mL distilled water and heated. After cooling, 15mL of hydrochloric acid (HCl, 37%) was slowly added to the solution and stirred for 30 minutes, after which the mixed solution was dried in an oven at 80 ℃. The dried sample is referred to as melamine hydrochloride. Subsequently, 10g of melamine hydrochloride was placed in a crucible with a lid and calcined in a muffle furnace at 550℃for 3 hours at a heating rate of 5℃per minute, and the resulting sample was porous g-C 3N4 (abbreviated as p-CN).
2. Phosphorus doped porous g-C 3N4（p-Px CN)
The phosphorus doped porous g-C 3N4 is synthesized by a thermal polymerization process. The specific steps are that 10g of melamine hydrochloride is uniformly mixed with a certain amount (0.5 g, 1g and 1.5 g) of hexachloromelamine. The mixture was placed in a covered crucible and calcined using a muffle furnace at 550 c for 3 hours at a heating rate of 5 c/min. The yellow powder obtained was phosphorus-doped porous g-C 3N4 (abbreviated as P-PxCN, x represents the addition of hexachloromelamine, and the above samples were designated P-P 0.5CN、p-P1 CN and P-P 1.5 CN, respectively).
3. Synthesis of Carbon Quantum Dots (CQDs)
Carbon Quantum Dots (CQDs) were prepared using a modified base-assisted ultrasound process. Specifically, 9.0g of glucose was uniformly dissolved in 50ml of deionized water, and then 50ml of aqueous ammonia (1 mol/L) was added and stirring was continued for 8 hours. Hydrochloric acid was added to adjust the stock solution to ph=7 and dialysis was performed through a semipermeable membrane (MWCO 3000). Finally, a clear brown solution, known as aqueous CQDs, was obtained. It is stored in a refrigerator at 4 ℃ for use.
4. Synthesis of composite photocatalyst P-P 1CN/CQDsy
CQDs are supported on P-P 1 CN by hydrothermal method. Specifically, 1.0g of P-P 1 CN and a certain amount (20 mL, 25mL, 30 mL) of CQDs solution were added to 50mL of deionized water, and stirred at room temperature for 6 hours. Thereafter, the mixed solution was transferred to an 80mL polytetrafluoroethylene-lined stainless steel autoclave and reacted at 180℃for 8 hours. The resulting samples were abbreviated as P-P 1CN/CQDsy (y is the amount of CQDs added, which are designated P-P 1CN/CQDs20、p-P1CN/CQDs25 and P-P 1CN/CQDs30, respectively).
For comparison, CQDs-loaded porous g-C 3N4 was also synthesized. The synthesis was similar to P-P 1CN/CODsy except that P-CN was added during the synthesis instead of P-P 1 CN, and the resulting sample was designated P-CN/CQDs y.
5. Photocatalytic experiments
The generation of photocatalytic H 2O2 was carried out at ambient temperature (25 ℃) and visible light was provided by a 300W Xe lamp, plus a 420nm cut-off filter. No sacrificial agent is added to the reaction system and no oxygen is exposed. Typically, a 0.8 g sample was added to 200 mL distilled water and stirred in the dark for 30 minutes to reach adsorption-desorption equilibrium, and then the reaction system was irradiated with visible light. During the irradiation, 5mL of the suspension was taken out of the reaction system at intervals, and filtered to remove the photocatalyst. The content of H 2O2 was analyzed by the potassium titanyl oxalate method. The H 2O2 produced can react with potassium titanium oxalate in an acidic medium to form a stable orange complex. The amount of orange complex was determined by ultraviolet-visible spectrum having a wavelength of 400nm, from which the concentration of H 2O2 produced was estimated [50]. In addition, the decomposition behavior of H 2O2 on the prepared samples was investigated under visible light at an initial concentration of 1.25mM for 60 minutes.
The crystal structure of the samples was analyzed by an aeies X-ray diffractometer (XRD) under copper target ka radiation (0.154178 nm). Morphology and microstructure were studied by Scanning Electron Microscopy (SEM) (JSM-6701F instrument, JEOL, japan) and Transmission Electron Microscopy (TEM) (JEM 2100 FS, JEOL, japan). Molecular structure was studied using a Nicolet Avatar-70 FTIR spectrometer (FT-IR) over a scan range of 400-4000cm -1. The chemical composition and state were measured by Thermo SCIENTIFIC K-Alpha X-ray photoelectron spectroscopy (XPS). Optical properties were studied using Shimadzu ultraviolet-visible Diffuse Reflectance Spectroscopy (DRS) (Shimadzu UV-2450 spectrophotometer) with BaSO 4 powder as a reflectance standard. Photoluminescence (PL) spectra were obtained using a irinotecan F-4500 spectrophotometer with a 150W xenon lamp as excitation source. The O 2 adsorption capacity of the samples was tested using Conta CHEMBET TPR/TPD by programmed temperature rising chemisorption (TPD-O 2). The radical intermediate was detected by electron spin resonance (EPR) on a bruck EMXPLUS spectrometer under visible light irradiation using 5, 5-dimethyl-L-pyrroline N-oxide (DMPO) as probe.
6. Characterization analysis
The crystal structure of the sample was analyzed by X-ray diffractometer (XRD). The morphology and microstructure of the samples were studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The molecular structure of the samples was studied using FTIR spectroscopy (FT-IR). The chemical composition and configuration were measured by X-ray photoelectron spectroscopy (XPS). Optical absorption was analyzed by ultraviolet-visible Diffuse Reflectance Spectroscopy (DRS). The separation and migration of photo-generated electron holes was analyzed by Photoluminescence (PL) spectroscopy and electrochemical testing. The adsorption capacity of the samples for O 2 was tested using temperature programmed chemisorption (TPD-O 2). The free radical intermediate was detected using electron spin resonance (EPR) under visible light irradiation.
As shown in FIG. 1, XRD results indicate that the scheme successfully synthesizes four photocatalysts of P-CN, P-P 1CN,p-P1CN/CQDs25 and P-CN/CQDs 25, and the four photocatalysts have two obvious characteristic peaks at the positions of 13.1 DEG and 27.5 DEG of 2 theta, which correspond to (100) crystal faces and (002) crystal faces of g-C 3N4 respectively, so that the structures of the g-C 3N4 are not obviously damaged by doped phosphorus and loaded carbon points. The TEM image of fig. 2 shows that p-CN exhibits a porous layered structure with non-uniform surface, while its microstructure is not substantially changed after doping with phosphorus. For P-P 1CN/CQDs25, the carbon quantum dots can be obviously and evenly distributed on the surface of P-P 1 CN, and the carbon dots show obvious lattice fringes, and the lattice spacing is 0.34 nm, which corresponds to the (002) crystal face of the carbon quantum dots. The UV-visible absorption results in FIG. 3 (a) show that doped phosphorus can broaden the visible response range of P-CN from 470nm to 475nm, and P-P 1CN/CQDs25 is greatly improved in both light absorption intensity and light absorption range after carbon point loading. Furthermore, the mott-schottky test of fig. 3 (b) shows that P-CN, P-P 1CN,p-P1CN/CQDs25 have conduction bands of-1.29, -1.26 and-1.16V (vs. RHE), respectively, whereas the XPS valence band spectrum of fig. 3 (c) shows P-CN, P-P 1CN,p-P1CN/CQDs25 have valence bands of 2.67, 2.66 and 2.61 eV, respectively. Theoretical calculated DOS plots of fig. 3 (d), (e) P-P 1 CN and P-P 1CN/CQDs25 show that for P-P 1 CN, both the s and P orbitals of P contribute to the valence band of the complex, while for P-P 1CN/CQDs25, in addition to the P orbitals contribute to the valence band of the complex, the P orbitals of C in CQDs also contribute to the valence band of the complex, indicating strong coupling between doped phosphorus and loaded carbon quantum dots. The P-CN, P-P 1CN,p-P1CN/CQDs25 energy band structure diagram is given according to the Mort-Schottky test and XPS valence band spectrum results, and the band gaps of the P-CN, P-P 1CN,p-P1CN/CQDs25 energy band structure diagram are respectively 2.67, 2.66 and 2.61 eV, as shown in fig. 3 (f). The PL results in fig. 4 (a) show that P-P 1 CN shows better photo-generated electron-hole separation efficiency than P-CN after doping with phosphorus. And after loading the carbon quantum dots, P-P 1CN/CQDs25 shows further improved photo-generated electron-hole separation efficiency. While P-CN/CQDs 25 exhibit similar photogenerated electron-hole separation efficiencies as P-P 1CN/CQDs25. However, as can be seen from the EIS results of fig. 4 (b), P-P 1 CN exhibits a smaller photo-generated carrier transport resistance than P-CN, while the photo-generated carrier transport resistance of P-P 1CN/CQDs25 is further reduced and smaller than that of P-CN/CQDs 25. Indicating that doped phosphorus plays a key role in carrier transport. To further demonstrate, the inventors also performed tests on the sample for transient photocurrents under different conditions (with or without fast electron scavengers (MVCl 2)), calculated the photogenerated electron transfer efficiencies, which showed that P-CN, P-P 1CN,p-P1CN/CQDs25 and P-CN/CQDs 25 had photogenerated electron transfer efficiencies of 66.7%, 67.6%, 86.4% and 74.7%, respectively, as shown in fig. 4 (c) and (d). The results show that both the doped phosphorus and the loaded carbon quantum dots increase the photon-generated electron transfer efficiency of the composite. Of note, the former has greater photo-generated electron transfer efficiency compared to P-P 1CN/CQDs25 and P-CN/CQDs 25, indicating that doped phosphorus acts as a bridge in photo-generated electron transfer, migrating photo-generated electrons to the loaded carbon quantum dots, which will greatly improve the performance of the composite in photocatalytic H 2O2 production. Thus, the inventors have conducted experiments for generating H 2O2 under light conditions using different samples, as shown in FIG. 5, and the results indicate that P-P 1CN/CQDs25 exhibits optimal photocatalytic activity, and that H 2O2 is generated up to 494. Mu.M/L after reaction 5H, which is 21 times and 14 times that of P-CN and P-P 1 CN, respectively. And the generation rate constant K f is 238 mu M h-1, 34 times and 22 times that of P-CN and P-P 1 CN, respectively. While for P-CN/CQDs 25, the amount of H 2O2 produced is only about 60% of that of P-P 1CN/CQDs25. In addition, experiments of producing H 2O2 by photocatalysis of P-P 1CN/CQDs25 under the illumination condition with the wavelength of more than 800nm show that P-P 1CN/CQDs25 still has certain photocatalytic activity, but P-P 1 CN does not show the photocatalytic activity, which is mainly based on the up-conversion performance of the loaded carbon quantum dots. We performed a decomposition experiment with H 2O2 (initial concentration of 1.25 mmol L −1) on the different samples, and the results showed that all samples exhibited a weaker decomposition rate constant for H 2O2, which was very beneficial for the photocatalytic production of H 2O2 from the complex. In addition, to demonstrate the advantages of using ammonia to prepare CQDs in the alkaline solution ultrasonic method, we have compounded CQDs prepared under different conditions with p-CN, and as can be seen from the results of FIG. 6, p-CN/CQDs 25 prepared from ammonia as alkaline solution show significantly superior H 2O2 production efficiency.

Claims (4)

1. The preparation method of the composite photocatalyst for efficiently generating hydrogen peroxide without adding any sacrificial agent under visible light is characterized by comprising the following steps:
1) Synthesis of phosphorus doped porous g-C 3N4
The porous g-C 3N4 doped with phosphorus is synthesized by adopting a thermal polymerization method: evenly mixing melamine hydrochloride and hexachloromelamine, wherein the mass ratio of the melamine hydrochloride to the hexachloromelamine is 10: x, wherein x is 0.5-1.5; placing the mixture in a crucible with a cover, calcining the mixture for 3-5 hours at a heating speed of 3-10 ℃/min at 530-560 ℃ by utilizing a muffle furnace, wherein the obtained yellow powder is porous g-C 3N4 doped with phosphorus, which is called P-P x CN for short, and x represents the addition amount of hexachloromelamine;
2) Synthesis of carbon quantum dots
Preparing carbon quantum dots by an alkali-assisted ultrasonic method: uniformly dissolving glucose in deionized water, adding ammonia water with the concentration of 1mol/L, carrying out ultrasonic treatment for 1.5-3 hours, and continuously stirring for 6-9 hours, wherein the concentration ratio of the glucose solution to the ammonia water is 0.5-1.5:1, and the volume ratio of the glucose solution to the ammonia water is 2:1-1:2; adding hydrochloric acid to adjust the pH value of the mixed solution to be 7, dialyzing through an MWCO 3000 semipermeable membrane to finally obtain a transparent brown solution, namely CQDs aqueous solution, and storing the transparent brown solution in a refrigerator at 4 ℃ for later use;
3) Synthesis of composite photocatalyst P-P xCN/CQDsy
CQDs are supported on P-P x CN by hydrothermal method: adding P-P x CN and CQDs solution into 30-80 mL deionized water, wherein the proportion relation is that 20-30 mL of CQDs solution is added into each gram of P-P x CN, stirring for 4-10 hours at room temperature, transferring the mixed solution into a polytetrafluoroethylene lining stainless steel autoclave, and reacting for 6-9 hours at 170-190 ℃, wherein the obtained sample is simply referred to as P-P xCN/CQDsy, and y is the addition amount of the CQDs solution;
The generation of the photocatalytic H 2O2 was carried out at an ambient temperature of 25℃with the visible light provided by a 300W Xe lamp, with a 420nm cut-off filter, and without the addition of sacrificial agents or oxygen exposure in the reaction system.
2. The method for preparing the composite photocatalyst capable of efficiently generating hydrogen peroxide without adding any sacrificial agent under visible light as claimed in claim 1, wherein x in the step (1) is 0.5,1 or 1.5; in the step (3), the value of y is 20mL, 25mL and 30mL.
3. The method for preparing the composite photocatalyst capable of efficiently generating hydrogen peroxide under visible light without adding a sacrificial agent according to claim 2, wherein x is 1.
4. The method for preparing a composite photocatalyst capable of efficiently generating hydrogen peroxide without adding any sacrificial agent under visible light as claimed in claim 3, wherein in the step (1), the composite photocatalyst is calcined at 550 ℃ for 3 hours at a heating rate of 5 ℃/min by using a muffle furnace; ultrasound is carried out for 2 hours in the step (2), and stirring is continued for 8 hours afterwards; the concentration ratio of the glucose solution to the ammonia water is 1:1, and the volume ratio of the glucose solution to the ammonia water is 1:1; the mixed solution in the step (3) was stirred at room temperature for 6 hours, and the mixed solution was transferred to an 80mL polytetrafluoroethylene-lined stainless steel autoclave and reacted at 180℃for 8 hours to obtain P-P 1CN/CQDs20、p-P1CN/CQDs25 and P-P 1CN/CQDs30.
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