CN112138694B - Graphite-phase carbon nitride/silver/biomass charcoal and preparation method and application thereof - Google Patents
Graphite-phase carbon nitride/silver/biomass charcoal and preparation method and application thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 description 22
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- 238000000034 method Methods 0.000 description 6
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- -1 1, 2-dichloroethylene, monochloroethylene, acetylene Chemical group 0.000 description 2
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Classifications
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a graphite-phase carbon nitride/silver/biomass charcoal and a preparation method and application thereof, wherein the preparation method comprises the following steps: g to C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Uniformly mixing to obtain a mixed material precursor, preserving the temperature of the mixed material precursor at 300-600 ℃ for 2-6h to obtain graphite phase carbon nitride/silver/biomass charcoal, and g-C under dark condition 3 N 4 、Ag 3 PO 4 Biomass charcoal and g-C 3 N 4 The adsorption balance of the/Ag/biochar on TCE can be realized in 10h under dark conditions, and the adsorption rates are respectively 13%, 9%, 20% and 40%. Compared with the single material, the adsorption rate of the composite material to TCE is improved by 2-4 times. g-C at 4h of visible light irradiation after adsorption equilibration 3 N 4 、Ag 3 PO 4 The catalytic degradation efficiency of the biomass charcoal and the graphite-phase carbon nitride/silver/biomass charcoal on TCE is 29%, 31%, 25% and 98% respectively. The analysis result of the degradation products shows that: the graphite phase carbon nitride/silver/biomass charcoal can realize the high-efficiency degradation of TCE, and the degradation product is CO 2 Mainly comprises the following steps.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and water treatment, and particularly relates to graphite-phase carbon nitride/silver/biomass charcoal and a preparation method and application thereof.
Background
Due to its wide application in the dry cleaning and automotive industries (cleaning and degreasing solvents), trichloroethylene (TCE) is the most common contaminant in various environmental substrates such as ground water, wastewater and soil. The U.S. toxic and disease registry (ATSDR) reported that TCE was found in 852 super-fund remediation sites in the United states. TCE can pose a significant hazard to public health and the ecosystem due to its toxicity, carcinogenicity, and biodegradability. The U.S. Environmental Protection Agency (EPA) ranks TCE as one of the 129 priority pollutants and specifies that its maximum concentration allowed to be detected in drinking water (MCL) is 5 μ g/L. Given the common nature of TCE and the persistence of the hazard, there is a great need to find a way to degrade TCE into harmless products. Chen et al investigated the effectiveness of zero-valent iron at pH 1.7-10 for TCE dechlorination (0.5 mmol/L), and found that 2.5mg/mL of zero-valent iron achieved the fastest dechlorination rate at pH 4.9. However, most of these processes result in partial degradation of TCE and the formation of toxic intermediates, including cis-1, 2-dichloroethylene, 1-dichloroethylene, and vinyl chloride. These intermediates not only have carcinogenic properties, but also tend to accumulate in the food chain. Therefore, it is very important to develop efficient techniques capable of completely degrading TCE.
Advanced oxidation processes, such as photocatalysis, photoozonation, photofenton technology, and combinations thereof, are of great interest for water pollutant removal. This depends mainly on their advantages of high degradation efficiency, environmental protection, low cost, low toxicity and easy handling. However, the single catalyst has the following disadvantages: lower spectral trapping efficiency, poor stability and electron-hole recombination. Therefore, the preparation of high-efficiency photocatalyst composite materials to overcome the defects is very important for the application of the photocatalytic technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of graphite phase carbon nitride/silver/biomass charcoal.
The invention also aims to provide the graphite-phase carbon nitride/silver/biomass charcoal obtained by the preparation method.
The purpose of the invention is realized by the following technical scheme.
A preparation method of graphite phase carbon nitride/silver/biomass charcoal comprises the following steps:
g to C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Uniformly mixing to obtain a mixed material precursor, and keeping the mixed material precursor at 300-600 ℃ for 2-6h to obtain graphite phase carbon nitride/silver/biomass charcoal, wherein g-C is calculated according to parts by weight 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The ratio of (1-5): (1-5): 1.
in the above technical scheme, the g-C 3 N 4 The precursor is melamine and/or urea.
In the above technical solution, the method for implementing uniform mixing includes: subjecting said g-C to 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Mixing, ball milling in the ball milling tank of planetary ball mill for 2-24 hr to obtain the product g-C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The mass sum of M is that the ratio of M to the grinding balls in the planetary ball mill is 1 (50-100) according to the mass parts, and the revolution speed of the planetary ball mill is 300-700 rpm during ball milling.
In the technical scheme, the heat preservation time is 4 hours.
In the technical scheme, the step of keeping the temperature of the mixed material precursor at 300-600 ℃ comprises the following steps: and placing the mixed material precursor into a furnace body, and heating to 300-600 ℃ at a speed of 1-5 ℃/min.
The graphite-phase carbon nitride/silver/biomass charcoal obtained by the preparation method.
The application of the graphite-phase carbon nitride/silver/biomass charcoal in degrading TCE.
In the technical scheme, the pH value of the TCE aqueous solution is adjusted to 5-9, and the graphite-phase carbon nitride/silver/biomass charcoal is put into the TCE aqueous solution.
In the technical scheme, the environment when the graphite-phase carbon nitride/silver/biomass charcoal degrades the TCE is under visible light irradiation or in a dark environment, and when the environment is in the dark environment, the TCE aqueous solution is continuously stirred during degradation.
In the technical scheme, the graphite-phase carbon nitride/silver/biomass charcoal is degraded in the dark for 10-24 hours and then degraded under the irradiation of visible light for 2-6 hours.
In the technical scheme, degradation products obtained after the graphite-phase carbon nitride/silver/biomass charcoal is used for degrading TCE are ethylene, carbon dioxide and water.
The invention has the following beneficial effects:
1. g-C in darkness 3 N 4 、Ag 3 PO 4 Biomass charcoal and g-C 3 N 4 The adsorption balance of the/Ag/biochar on TCE can be realized in 10h under dark conditions, and the adsorption rates are respectively 13%, 9%, 20% and 40%. The adsorption rate of the composite material to TCE is improved compared with that of the single material2 to 4 times.
2. g-C at 4h of visible light irradiation after adsorption equilibrium 3 N 4 、Ag 3 PO 4 The catalytic degradation efficiency of the biomass charcoal and the graphite-phase carbon nitride/silver/biomass charcoal on TCE is 29%, 31%, 25% and 98% respectively. The analysis result of the degradation product shows that: the graphite-phase carbon nitride/silver/biomass charcoal can realize high-efficiency degradation of TCE, and the degradation product is CO 2 Mainly comprises the following steps.
3. g-C compared with the prior art 3 N 4 The Ag/biochar can realize high-efficiency degradation (98%) of TCE in the' iron-doped nano TiO 2 In the research of degrading trichloroethylene by visible light gas phase, iron is doped with nano TiO 2 The removal rate of TCE is only about 40%, and the addition amount is far larger than that of the invention (0.5 g).
Drawings
FIG. 1 shows the TCE degradation efficiency (TCE removal rate) in examples 22 to 26 of the present invention;
FIG. 2 shows the TCE degradation efficiency of different materials to be tested in example 27 of the present invention;
FIG. 3 shows the degradation product ratios obtained for different materials to be tested in example 28 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The sources of the drugs in the following examples are as follows:
analytically pure Ag 3 PO 4 Urea and melamine were purchased from feng boat chemical ltd (china, tianjin).
Trichloroethylene (TCE), 1, 2-dichloroethylene (cis-DCE), trans-1, 2-dichloroethylene (trans-DCE), 1-dichloroethylene (1, 1-DCE) and Vinyl Chloride (VC) were purchased from J & K, china chemical Co., ltd.
Sodium hydroxide (NaOH) and hydrochloric acid (HCl) (used to adjust the experimental pH) were purchased from tianjin chemical reagents, inc.
In the following examples, in order to stir uniformly, in the dark adsorption experiment, a reciprocating vibrator was used, namely: the bottles were mixed on a reciprocating shaker at 180rpm (the mixing speed was not so high as to be uniform).
The following examples were carried out to test the TCE concentration after sampling: 5mL of the reaction solution was collected, centrifuged (4000rpm, 5 min), and the supernatant obtained by centrifugation was filtered through a 0.22 μm nylon membrane (Shanghai' an spectral laboratory science Co., ltd.), and the TCE concentration after filtration was determined by HPLC (Waters 1525, waters, milford Massachusetts, USA) equipped with a 2487UV detector and a Thermal Scientific C18 column (250X 4.6 mm). The mobile phase consisted of 70wt% acetonitrile and 30wt% deionized water, flow rate was 1.0mL/min, and column temperature was 30 ℃. The measurement wavelength was 214nm, the sample injection amount was 80. Mu.L, and the detection limit was 0.2mg/L. The concentrations of 1, 2-dichloroethylene, monochloroethylene, acetylene and ethylene as dechlorinated products were determined by Gas Chromatography (GC) (6850 Agilent HP, CA, USA). After the reaction was completed, 1.0mL of the reaction solution was taken out of the reaction flask with a gas-tight glass syringe, the same volume of deoxygenated Tris buffer solution was added, and transferred to a headspace flask containing 5mL of water to analyze the concentrations of 1, 2-dichloroethylene, monochloroethylene, acetylene and ethylene. The headspace vials were equilibrated in an autosampler at 85 ℃ for 20 minutes. The carrier gas from the autosampler was first passed through a DB-624 column (30 μm x 0.53mm i.d., with a 3 μm film thickness) and then the stream was resolved into a second DB-624 column connected to the ECD and a GS-Q column connected to the FID (30 m x 0.5mm i.d.). Heating according to the following flow: the temperature is kept constant at 40 ℃ for 10 minutes, the temperature is increased to 90 ℃ at 5 ℃/minute, the temperature is increased to 220 ℃ at 15 ℃/minute, and the temperature is kept constant at 220 ℃ for 5 minutes. ( The procedure for testing the TCE concentration after sampling can also be found in particular in: H.Lyu, J.Tang, B.Shen, T.Siddique, development of a novel chem-bio hybrid process using biochar supported nanoscale complex and Corynebacterium variabilium var variabilie HRJ4for enhanced trichloromethylene chloride, water Res.147 (2018) 132-141. )
The TCE concentration in the TCE aqueous solution before degradation is the initial concentration of TCE (C) 0 )。
TCE removal rate (%) = (C) 0 -Ce)*100/C 0 Wherein, C e The concentration of TCE in the aqueous solution of TCE after degradation.
In the following examples, g-C 3 N 4 System of (2)The preparation method comprises the following steps: g to C 3 N 4 Placing the precursor in a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and then preserving heat at 300 ℃ for 4h to obtain g-C 3 N 4 Wherein g-C 3 N 4 The precursor is urea.
In the following examples, the preparation method of biomass charcoal is: and (3) placing the pine sawdust in a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and then preserving heat at 300 ℃ for 4h to obtain the biomass charcoal.
It is to be understood that the following embodiments are merely illustrative of the present invention and do not limit the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the principle of the invention, and these changes and modifications also fall into the scope of the invention. The experimental method without specifying the specific conditions in the following embodiments is generally conducted under the usual conditions.
Examples 1 to 5
A preparation method of graphite phase carbon nitride/silver/biomass charcoal comprises the following steps:
g to C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Uniformly mixing to obtain a mixed material precursor g-C 3 N 4 The precursor is urea. Placing the mixed material precursor in a muffle furnace, heating to T ℃ at the speed of 5 ℃/min, and then preserving heat at the T ℃ for 4h to obtain graphite-phase carbon nitride/silver/biomass charcoal, wherein g-C is calculated according to parts by weight 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The values of (1).
The realization method of uniform mixing comprises the following steps: g to C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Mixing, ball milling in ball milling pot of planetary ball mill for 12h 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The mass sum of M is 1, the ratio of M to the grinding balls in the planetary ball mill is 100, and the revolution speed of the planetary ball mill during ball milling is 500rpm.
TABLE 1
| Examples | T (Unit:. Degree. C.) | Code of graphite phase carbon nitride/silver/biomass charcoal |
| Example 1 | 250 | g-C 3 N 4 /Ag/biochar250 |
| Example 2 | 300 | g-C 3 N 4 /Ag/biochar300 |
| Example 3 | 450 | g-C 3 N 4 /Ag/biochar450 |
| Example 4 | 600 | g-C 3 N 4 /Ag/biochar600 |
| Example 5 | 700 | g-C 3 N 4 /Ag/biochar700 |
The graphite phase carbon nitride/silver/biomass char obtained in examples 1 to 5 was tested for its effect on TCE removal.
Preparing 5 parts of TCE aqueous solution with pH of 7 and TCE concentration of 10mg/L, mixing g-C 3 N 4 /Ag/biochar250、g-C 3 N 4 /Ag/biochar300、g-C 3 N 4 /Ag/biochar450、g-C 3 N 4 Ag/biochar600 and g-C 3 N 4 adding/Ag/biochar 700 into 50mL of TCE aqueous solution respectively to obtain reaction solutions, and carrying out catalytic reaction on the reaction solutions for 6h under visible light (300W xenon lamp), wherein the concentration of graphite-phase carbon nitride/silver/biomass charcoal in the reaction solutions is 0.12g/L, after the reaction is finished, testing the removal rate of TCE, and the removal effect of TCE is shown in Table 2.
TABLE 2
Examples 6 to 21
Preparing a TCE aqueous solution (pH = 7) with the TCE concentration of 10mg/L, adding N g of a material to be detected into 50mL of the TCE aqueous solution to obtain a reaction solution, wherein the material to be detected is g-C 3 N 4 、Ag 3 PO 4 Biomass charcoal or the graphite phase carbon nitride/silver/biomass charcoal prepared in example 2. The N values are shown in Table 3. The reaction solution was magnetically stirred in the dark for 12h to ensure that an adsorption-desorption equilibrium was established between the TCE and the photocatalyst. After dark adsorption-desorption equilibrium, after irradiation for 4 hours under visible light (300W xenon lamp), after the reaction is finished, the removal rate of TCE is tested, and the test results are shown in Table 3, so that the degradation rate of graphite-phase carbon nitride/silver/biomass carbon to TCE is improved from 71% to 99% and is far higher than g-C 3 N 4 、Ag 3 PO 4 And biomass char (table 3). When the adding amount is 0.0500g, the degradation rate of the graphite phase carbon nitride/silver/biomass charcoal on TCE reaches 98 percent, and when the adding amount is 0.0500g, g-C 3 N 4 、Ag 3 PO 4 And the degradation rates of the biomass charcoal to TCE are respectively 30%, 50% and 19%. Therefore, from the viewpoint of cost saving, 0.0500g is most suitable, and further increase in the amount of material to be added is not required.
TABLE 3
| Examples | N (unit: g) | Material to be tested | TCE removal rate (unit:%) |
| Example 6 | 0.0050 | Graphite phase carbon nitride/silver/biomass charcoal | 71 |
| Example 7 | 0.0100 | Graphite phase carbon nitride/silver/biomass charcoal | 84 |
| Example 8 | 0.0500 | Graphite phase carbon nitride/silver/biomass charcoal | 98 |
| Example 9 | 0.1000 | Graphite phase carbon nitride/silver/biomass charcoal | 99 |
| Example 10 | 0.0050 | g-C 3 N 4 | 21 |
| Example 11 | 0.0100 | g-C 3 N 4 | 24 |
| Example 12 | 0.0500 | g-C 3 N 4 | 30 |
| Example 13 | 0.1000 | g-C 3 N 4 | 38 |
| Example 14 | 0.0050 | Ag 3 PO 4 | 32 |
| Example 15 | 0.0100 | Ag 3 PO 4 | 45 |
| Example 16 | 0.0500 | Ag 3 PO 4 | 50 |
| Example 17 | 0.1000 | Ag 3 PO 4 | 61 |
| Example 18 | 0.0050 | |
12 |
| Example 19 | 0.0100 | Biomass charcoal | 13 |
| Example 20 | 0.0500 | Biomass charcoal | 19 |
| Example 21 | 0.1000 | |
20 |
Examples 22 to 26
Preparing a TCE aqueous solution with the TCE concentration of 10mg/L, adding 0.0500g of graphite-phase carbon nitride/silver/biomass charcoal into 50mL of the TCE aqueous solution to obtain a reaction solution, adjusting the pH of the TCE aqueous solution to P by 0.01M HCl aqueous solution or 0.01M NaOH aqueous solution, and showing the value of P in Table 4. The reaction solution was magnetically stirred in the dark for 12h to ensure that an adsorption-desorption equilibrium was established between the TCE and the photocatalyst. After the dark adsorption-desorption equilibrium, after irradiation with visible light (300W xenon lamp) for 4 hours, the removal rate of TCE was measured after the reaction was completed, and the measurement results are shown in fig. 1, from which it was found that the graphite-phase carbon nitride/silver/biomass charcoal exhibited the best catalytic effect on TCE when the pH of the reaction solution was 7.
TABLE 4
| Examples | P |
| Example 22 | 3 |
| Example 23 | 5 |
| Example 24 | 7 |
| Example 25 | 9 |
| Example 26 | 11 |
Example 27
A TCE aqueous solution (pH 7) having a TCE concentration of 10mg/L was prepared, and 0.500g of a material to be measured was added to 500mL of the TCE aqueous solution to obtain a reaction solution. The reaction solution was magnetically stirred in the dark for 12h (time period-12 h-0 h in FIG. 2) to ensure that an adsorption-desorption equilibrium was established between TCE and the photocatalyst. After the dark adsorption-desorption equilibrium, the solution is irradiated for 4 hours (0 h-4 h time in figure 2) under visible light (300W xenon lamp)Segment), 5mL of the reaction solution was collected at regular intervals, and the TCE removal rate of the reaction solution collected each time was measured, and the measurement results are shown in fig. 2, in which the material to be measured was g-C 3 N 4 、Ag 3 PO 4 Biomass charcoal or the graphite phase carbon nitride/silver/biomass charcoal prepared in example 2.
As can be seen from fig. 2, the removal rate of TCE by graphite-phase carbon nitride/silver/biomass charcoal was the highest both in dark adsorption and visible light irradiation (maximum value of dark adsorption was 40% and maximum value of removal under visible light irradiation was 98%). g-C in darkness 3 N 4 、Ag 3 PO 4 Biomass charcoal and g-C 3 N 4 The adsorption balance of the/Ag/biochar (graphite phase carbon nitride/silver/biomass carbon) on TCE can be realized in 10h under dark condition, and the adsorption rate is respectively 13% (g-C) 3 N 4 )、9％(Ag 3 PO 4 ) 20% (Biomass char) and 40% (g-C) 3 N 4 Ag/biochar). Compared with the single material, the adsorption rate of the graphite phase carbon nitride/silver/biomass carbon as the composite material to TCE is improved by 2-4 times. After the visible light is irradiated, the degradation effect of the graphite-phase carbon nitride/silver/biomass charcoal on TCE is remarkably improved, which shows that the graphite-phase carbon nitride/silver/biomass charcoal has higher spectrum capture efficiency and overcomes the defect of electron-hole recombination of the original single material to a certain extent. The removal rate (degradation rate) of the graphite-phase carbon nitride/silver/biomass charcoal to TCE after 4h of photocatalysis is 98%, which is far greater than that of three single materials (g-C) in the same dosage 3 N 4 、Ag 3 PO 4 And biomass charcoal) in a total of 85% (Ag) 3 PO 29%, g-C 3 N 4 31% and 25% biomass char). It can be seen that the three materials for synthesizing the graphite phase carbon nitride/silver/biomass char of the present invention exhibit a synergistic effect when prepared into graphite phase carbon nitride/silver/biomass char, rather than a simple superposition of the materials.
Example 28
Preparing TCE aqueous solution (pH 7) with TCE concentration of 10mg/L, and adding 0.0500g of material to be detected into 50mL of TCE aqueous solution to obtain reaction solution, wherein the material to be detected is g-C 3 N 4 、Ag 3 PO 4 Biomass charcoal or the graphite phase carbon nitride/silver/biomass charcoal obtained from example 2. The reaction solution was magnetically stirred in the dark for 12h to ensure that an adsorption-desorption equilibrium was established between the TCE and the photocatalyst (material to be tested). After dark adsorption-desorption equilibrium, the photocatalytic reaction was carried out by irradiation for 4 hours under visible light (300W xenon lamp). After the reaction, the TCE removal rate was tested, the main degradation products in the filtered liquid were detected by gas chromatography-mass spectrometry (GC), and the concentration of the degradation products was converted to the percentage ratio, and the result is shown in fig. 3.
Table 5 shows the concentrations of the degradation products obtained in example 28. From FIGS. 3 and 5, it can be seen that ethylene is the main degradation product after the TCE is degraded by the graphite phase carbon nitride/silver/biomass charcoal, and although the ethylene ratio is 100%, the concentration is only 2mg/L, which indicates that the TCE can be completely degraded by the composite material except for ethylene H 2 O and CO 2 . Other single materials g-C compared to graphite phase carbon nitride/silver/biomass charcoal 3 N 4 、Ag 3 PO 4 And the degradation products of TCE by biochar (biochar) mainly comprise 1, 2-dichloroethylene (cis-DCE), 1-dichloroethylene (1, 1-DCE) and Vinyl Chloride (VC), and the intermediate products not only have carcinogenicity, but also are easy to accumulate in the food chain. Thus, the graphite phase carbon nitride/silver/biomass charcoal of the present invention achieves complete degradation of TCE.
TABLE 5
Claims (5)
1. The application of the graphite-phase carbon nitride/silver/biomass charcoal in the degradation of TCE is characterized in that the pH value of a TCE aqueous solution is adjusted to 5-9, the graphite-phase carbon nitride/silver/biomass charcoal is put into the TCE aqueous solution, and degradation products obtained after the graphite-phase carbon nitride/silver/biomass charcoal degrades the TCE are ethylene, carbon dioxide and water;
the preparation method of the graphite phase carbon nitride/silver/biomass charcoal comprises the following steps:
g to C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 Mixing, putting the mixture into a ball-milling tank of a planetary ball mill, and ball-milling the mixture for 2 to 24 hours to obtain a mixed material precursor, and keeping the temperature of the mixed material precursor at 300 to 600 ℃ for 2 to 6 hours to obtain graphite-phase carbon nitride/silver/biomass carbon, wherein g-C is calculated according to the mass fraction 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The ratio of (1-5): (1-5): 1, said g-C 3 N 4 Precursor, pine wood dust and Ag 3 PO 4 The mass sum of M is that the ratio of M to the grinding balls in the planetary ball mill is 1 (50-100) in parts by mass, and the revolution speed of the planetary ball mill is 300-700 rpm during ball milling.
2. Use according to claim 1, wherein said g-C is 3 N 4 The precursor is melamine and/or urea.
3. The application of claim 2, wherein the mixed material precursor is subjected to heat preservation at 300-600 ℃ by the following steps: and placing the mixed material precursor into a furnace body, and heating to 300-600 ℃ at a speed of 1-5 ℃/min.
4. The use according to claim 3, wherein the environment in which the graphitic carbon nitride/silver/biomass char degrades TCE is under visible light or in the dark, and when the environment is in the dark, the aqueous TCE solution is continuously stirred during degradation.
5. The use of claim 4, wherein the graphite-phase carbon nitride/silver/biomass charcoal degrades TCE in the dark for 10-24h, and then degrades under visible light for 2-6h.
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