CN115121275A - Preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, product and application thereof, and organic pollutant degradation method - Google Patents
Preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, product and application thereof, and organic pollutant degradation method 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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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 relates to the technical field of water treatment, in particular to a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, a product and an application thereof, and an organic pollutant degradation method. The preparation method comprises the following steps: dissolving melamine and ammonium sulfate in a solvent to obtain a precursor mixed solution; drying the precursor mixed solution to obtain a carbon nitride precursor; and calcining the carbon nitride precursor to obtain the carbon-oxygen co-doped graphite-phase carbon nitride. The preparation method has the advantages of simple and convenient synthesis method, low raw material cost, less energy consumption, short time consumption, easily-controlled conditions and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization. The obtained product has the advantages of high specific surface area, high photoproduction charge separation efficiency, high photocatalytic activity and the like, can efficiently degrade organic wastewater, and is a novel visible light catalyst.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, a product and an application thereof, and an organic pollutant degradation method.
Background
Antibiotics are compounds used to treat microbial infectious diseases. However, studies have confirmed that only a small part of antibiotics used in humans and animals is metabolized or absorbed in vivo, and about 40% to 90% of the antibiotics are excreted in vitro in the form of the original drug or primary metabolite through urine or feces. The consequence of high antibiotic consumption, incorrect drug treatment methods, excretion by humans and animals is that large amounts of antibiotics and their metabolites and conversion products enter the sewage system. However, at present, sewage treatment plants have limited treatment efficiency for antibiotics, resulting in large quantities of antibiotics being discharged directly into the environment, particularly in aquatic environments. Since aquatic organisms are exposed to water-borne pollutants throughout their life cycles, antibiotics have bactericidal or bacteriostatic effects, which may result in the disappearance of some microbial populations and their ecological functions, and even harm to human safety. Therefore, it is necessary to remove antibiotics from water to reduce the pollution of water environment. The traditional method for treating pollutants in water has limited technical means, such as a physical method, a chemical oxidation method, a chemical electrolysis method, a physical-chemical method, a biological method and the like, and the effect of completely degrading organic pollutants in water is difficult to achieve.
The advanced oxidation technology can generate a large amount of free radicals with strong oxidizing property, and the high-activity free radicals are utilized to attack macromolecular organic matters and react with the macromolecular organic matters, so that the molecular structure of the oil agent is damaged, the aim of removing organic pollutants by oxidation is fulfilled, and efficient oxidation treatment is realized.
The traditional advanced oxidation technology is to use hydroxyl radical (OH, E) 0 1.8-2.4V) to degrade pollutants. Hydroxyl radicals can rapidly and nonselectively degrade most organic pollutants in water, but the hydroxyl radicals need to react under acidic conditions, so that the hydroxyl radicals have some limitations. In recent years, persulfate is widely applied to advanced oxidation technology, and has the advantages of good stability, high solubility, various activation modes, wide application range and the like, and the generated SO 4 ·– The service life is longer, the full contact with pollutants is facilitated, and the effect of degrading the pollutants is greatly improved, so that the persulfate gradually becomes a novel advanced oxidation technology with good application prospect. Using SO4 ·– The key to oxidizing organic contaminants in water is how to activate the persulfate. Conventional methods can activate persulfate to produce sulfate radicals by heat, UV, transition metal ions, and the like. Due to the characteristics of high cost, high energy consumption and the like of a physical method and the defects of poor reutilization property, secondary pollution and the like when the persulfate is activated by the transition metal and is used for degrading organic matters by a chemical method. Therefore, the development of a novel photocatalyst for activating persulfate becomes a research hotspot of environmental workers.
Graphite phase carbon nitride (g-C) 3 N 4 ) The photocatalyst has the advantages of visible light activity, proper energy band position, good chemical stability and thermal stability and the like, and is considered to be a photocatalyst with great potential. However g-C 3 N 4 The visible light wavelength response of less than 460nm, the low dielectric property and the high resistivity of the material lead to the limitation of the visible light utilization and the high recombination rate of photo-generated charge carriers, and seriously affect the photocatalytic performance of the material.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, a product and application thereof, and an organic pollutant degradation method.
The invention provides a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, which at least comprises the following steps:
s1, dissolving melamine and ammonium sulfate in a solvent to obtain a precursor mixed solution;
s2, drying the precursor mixed solution to obtain a carbon nitride precursor;
and S3, calcining the carbon nitride precursor to obtain carbon-oxygen co-doped graphite-phase carbon nitride.
The invention also provides carbon-oxygen co-doped graphite-phase carbon nitride prepared by the method.
The invention also provides the application of the carbon-oxygen co-doped graphite-phase carbon nitride as a photocatalyst in activating persulfate to degrade organic wastewater; preferably, the mass ratio of the carbon-oxygen co-doped graphite-phase carbon nitride to the persulfate is 1: 0.1 to 5; more preferably, the organic wastewater contains antibiotic pollutants.
The invention also provides a method for degrading organic pollutants, which at least comprises the following steps:
s1, adding the carbon-oxygen co-doped graphite-phase carbon nitride into the organic pollutant wastewater to be treated, and stirring under a dark condition;
and S2, adding persulfate, and degrading the organic pollutants under the visible light condition.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the following advantages:
the invention provides a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride and a product, and the preparation method has the advantages of simple and convenient synthesis method, low raw material cost, less energy consumption, short time consumption, easily-controlled conditions and the like, is suitable for continuous large-scale batch production, and is convenient for industrial utilization. The obtained product has the advantages of high specific surface area, high photoproduction charge separation efficiency, high photocatalytic activity and the like, can efficiently degrade organic wastewater, and is a novel visible light catalyst.
The invention provides an application of carbon-oxygen co-doped graphite-phase carbon nitride as a photocatalyst in activating persulfate to degrade organic wastewater, and the release of active substances in a persulfate oxidation system is promoted by adjusting the ratio of the carbon-oxygen co-doped graphite-phase carbon nitride to the persulfate.
The invention also provides a degradation method of organic pollutant wastewater, wherein carbon-oxygen co-doped graphite-phase carbon nitride is used as a photocatalyst to catalyze persulfate, and the process parameters are adjusted to promote the complete degradation of the organic pollutant wastewater.
Drawings
FIG. 1 shows g-C 3 N 4 And XRD patterns of CO-CN;
FIG. 2 shows g-C 3 N 4 And Fourier Infrared Spectroscopy (FTIR) plots of CO-CN;
FIG. 3 is g-C 3 N 4 SEM picture of (1);
FIG. 4 is an SEM image of CO-CN;
FIG. 5 is g-C 3 N 4 XPS survey before and after use with CO-CN;
FIG. 6 shows g-C 3 N 4 C1s spectra before and after use with CO — CN;
FIG. 7 is g-C 3 N 4 N1s spectra before and after use with CO — CN;
FIG. 8 is g-C 3 N 4 O1s spectra before and after use with CO — CN;
FIG. 9 shows g-C 3 N 4 And UV-Vis plot of CO-CN;
FIG. 10 is a graph of the effect of CO-CN of different solvents on OTC degradation;
FIG. 11 shows the effect of CO-CN with different precursor ratios on OTC degradation;
FIG. 12 is a graph of the effect of CO-CN dosing on OTC degradation;
FIG. 13 is the effect of initial pH on OTC degradation;
FIG. 14 shows the cyclic degradation experiment of CO-CN on OTC.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
The first aspect of the embodiment of the invention provides a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, which adopts the technical means of calcining melamine and ammonium sulfate to obtain a precursor and then calcining the precursor. The preparation method at least comprises the following steps:
s1, dissolving melamine and ammonium sulfate in a solvent to obtain a precursor mixed solution;
s2, drying the precursor mixed solution to obtain a carbon nitride precursor;
and S3, calcining the carbon nitride precursor to obtain carbon-oxygen co-doped graphite-phase carbon nitride.
In a preferred embodiment of the present invention, in S1, the molar ratio of melamine to ammonium sulfate is 0.1 to 10: 1, preferably 0.5-5: 1. the embodiment of the invention explores the influence of different proportions of ammonium sulfate and melamine on photocatalytic performance, and comprehensively prepares the yield, wherein the molar ratio of the melamine to the ammonium sulfate is 0.8-2: 1, most preferably 1 to 1.5: 1.
as a preferred technical solution of the embodiment of the present invention, in S1, the solvent is selected from a solvent capable of dissolving melamine and ammonium sulfate, and water or an organic solvent may be selected, and in order to reduce the amount of the solvent used, an organic solvent with high solubility of melamine and ammonium sulfate, such as an alcohol organic solvent or a sulfone organic solvent, is further preferred; the alcohol organic solvent is further selected from absolute ethyl alcohol, and the sulfone organic solvent is further preferably dimethyl sulfoxide. During the dissolution process, the dissolution can be accelerated by means of the prior art, such as stirring, ultrasound, etc., and the specific conditions can be selected according to common knowledge.
Further, in S1, the amount of the solvent used is not particularly limited, so that melamine and ammonium sulfate can be completely dissolved.
As a preferred embodiment of the present invention, in S2, the drying method includes: heating and drying while stirring; wherein the stirred target raw materials are fully contacted to form a supermolecular polymer precursor. The stirring speed is 150 r/min-350 r/min, and preferably 200 r/min-300 r/min. The precursor mixed solution is heated to 30-90 ℃, preferably to 30-60 ℃, and if the heating temperature is too high, the supermolecular polymer structure can be damaged, so that the catalytic activity of the carbon-oxygen co-doped graphite-phase carbon nitride product is reduced.
As a preferred embodiment of the present invention, in S2, there is a grinding step after obtaining the precursor. The grinding conditions are not particularly limited, and the powder may be ground in a mortar.
As a preferred technical scheme of the embodiment of the invention, in step S3, the heating rate of calcination is 2-10 ℃/min; the calcination temperature is 350-600 ℃, preferably 500-550 ℃, and most preferably 550 ℃; the temperature mainly influences the shape and structure of the carbon-oxygen co-doped graphite-phase carbon nitride product; essentially a bulk structure if the temperature is too low; if the temperature is too high, the formed pore structure may collapse. The calcination time is 2 to 12 hours, preferably 2 to 8 hours, and more preferably 2 to 4 hours.
As a preferred technical solution of the embodiment of the present invention, in S3, after the carbon-oxygen co-doped graphite-phase carbon nitride is obtained by calcination, a grinding step is further included. The grinding conditions are not particularly limited, and the powder may be ground in a mortar.
The second aspect of the embodiment of the invention provides carbon-oxygen co-doped graphite-phase carbon nitride prepared by the method. XRD (X-ray diffraction) characterization, FTIR (FTIR) characterization, SEM (scanning Electron microscope) characterization and XPS (X-ray diffraction) characterization prove that carbon atoms and oxygen atoms are simultaneously doped in the graphite phase carbon nitride, and that the carbon-oxygen co-doped graphite phase carbon nitride is obtained. According to UV-vis analysis, the carbon-oxygen co-doped graphite-phase carbon nitride has stronger light absorption capacity and can generate more photo-generated electron and hole pairs.
The third aspect of the embodiment of the invention provides an application of the carbon-oxygen co-doped graphite-phase carbon nitride as a photocatalyst in degrading organic wastewater by activating persulfate. As a preferable technical scheme of the embodiment of the invention, after screening, the mass ratio of the carbon-oxygen co-doped graphite-phase carbon nitride to the persulfate is 1: 0.1 to 5, preferably 1: 0.5 to 2.5, most preferably 1: 1.
as a preferred embodiment of the present invention, the organic wastewater contains antibiotic contaminants, such as tetracycline hydrochloride or ciprofloxacin, but is not limited thereto. As mentioned above, antibiotic organic pollutants have strong environmental pollution and are widely available, and are difficult to completely decompose by other water treatment methods.
A fourth aspect of the embodiments of the present invention provides a method for degrading organic pollutants, including at least the following steps:
s1, adding the carbon-oxygen co-doped graphite-phase carbon nitride into the organic pollutant wastewater to be treated, and stirring under a dark condition;
s2, adding persulfate, and degrading the organic pollutants under the visible light condition, wherein the persulfate is specifically Peroxymonosulfate (PMS).
As a preferable technical scheme of the embodiment of the invention, in S1, the initial concentration of the organic pollutants in the wastewater is 5 mg/L-50 mg/L.
As a preferable technical scheme of the embodiment of the invention, researches show that under the coordination of PMS, an alkaline environment has a better activation effect on PMS, the degradation rate on organic pollutants is higher, and the pH value of wastewater can be 7-14, preferably 8-12, and more preferably 9-10.
In S1, stirring for 30-90 min; the stirring speed is 150-350 r/min. The stirring can make the catalyst fully contact with pollutants, is favorable for mass transfer and further is favorable for catalysis.
As an optimal technical scheme of the embodiment of the invention, in S1, the concentration of carbon-oxygen co-doped graphite-phase carbon nitride in organic pollutant wastewater is 0.01-0.5 g/L, and preferably 0.1-0.5 g/L. In S2, the concentration of persulfate in the organic pollutant wastewater is 0.1-2 g/L, and preferably 0.1-0.5 g/L.
As a preferred technical solution of the embodiment of the present invention, in S2, the degradation time is 1 to 180min, preferably 30 to 90min, and more preferably 45 to 90min, which can be specifically adjusted according to the total amount of sewage and the catalyst concentration. In the practical application process, 60% of oxytetracycline hydrochloride can be degraded within 2-4 minutes from the beginning of degradation.
In S2, the intensity of the visible light is not particularly limited, and is preferably a 300W xenon lamp light source, λ >420 nm.
The method for degrading organic pollutants according to the embodiment of the invention is carried out at normal temperature.
The technical scheme and technical effect of the embodiment of the invention are further illustrated by the following embodiments and experimental examples. The raw materials used in the examples and experimental examples of the invention are all commercially available, and the instruments and equipment used are all existing instruments and equipment.
Example 1:
the embodiment provides a preparation method of carbon-oxygen co-doped graphite-phase carbon nitride, which comprises the following steps:
(1) according to the mol ratio of ammonium sulfate to melamine of 1: 1, respectively adding the weighed ammonium sulfate and melamine into dimethyl sulfoxide (the total volume of the used dimethyl sulfoxide is 80mL), and carrying out ultrasonic treatment to completely dissolve the ammonium sulfate and the melamine into the dimethyl sulfoxide to obtain a mixed solution of the ammonium sulfate and the melamine.
(2) And (2) heating the mixed solution of ammonium sulfate and melamine obtained in the step (1) to 30 ℃ in a constant-temperature water bath, keeping the temperature constant, volatilizing the solvent under the condition of electric stirring at the rotating speed of 250r/min, and marking the white product obtained after the solvent is volatilized as a carbon nitride precursor.
(3) And (3) grinding the carbon nitride precursor obtained in the step (2), transferring the carbon nitride precursor into a ceramic crucible, then placing the ceramic crucible into a tubular furnace, calcining the ceramic crucible for 4 hours at the temperature rising speed of 2.5 ℃/min to 550 ℃, naturally cooling the ceramic crucible to room temperature, and grinding the ceramic crucible to obtain carbon-oxygen co-doped graphite-phase carbon nitride, wherein the number of the carbon-oxygen co-doped graphite-phase carbon nitride is A1.
In inventive example 1, under the same conditions, when the ratio of the amounts of the substances of ammonium sulfate and melamine in step (1) is 1.5: 1. 1: 2, the prepared carbon-oxygen co-doped graphite phase carbon nitride is respectively numbered A2 and A3.
When the solvent in the step (1) is selected from water and absolute ethyl alcohol, the prepared carbon-oxygen co-doped graphite-phase carbon nitride is respectively numbered as B1 and B2.
Experimental example 1
This experimental example is used for the carbon oxygen codope graphite phase carbon nitride A1 who obtains the preparation and characterizes:
hereinafter, for the sake of brevity of the description, g-C 3 N 4 Indicating undoped graphite phase carbon nitride and CO-CN indicating carbon-oxygen CO-doped graphite phase carbon nitride.
1. XRD characterization
In order to examine the crystal structure of carbon-oxygen co-doped graphite-phase carbon nitride, an X-ray diffractometer (XRD) is adopted for g-C 3 N 4 Was characterized with CO-CN. The results are shown in FIG. 1.
As can be seen in FIG. 1, g-C 3 N 4 The spectrum with CO-CN has two typical diffraction peaks at 13.1 ℃ and 27.6 ℃ respectively corresponding to g-C 3 N 4 The (100) and (002) crystal planes of (a). The intensity of the diffraction peak of the crystal face of CO-CN is relatively larger, which shows that the carbon-oxygen element and g-C 3 N 4 The successful combination of the photocatalyst improves the crystallinity of the photocatalyst.
2. Characterization by FTIR
The FTIR characterization results are shown in fig. 2.
As shown in FIG. 2, both photocatalysts showed a characteristic peak of graphite-phase carbon nitride of 900cm -1 ～1800cm -1 The broad peak of the range is attributed to CN heterocyclic characteristic stretching vibration; located at 807cm -1 The characteristic peak of (A) is attributed to the bending vibration of the molecular skeleton outside the triazine ring.
3. SEM characterization
Scanning Electron Microscopy (SEM) for g-C 3 N 4 The surface morphology of the material and CO-CN is characterized.
As shown in FIG. 3, g-C 3 N 4 The structure is a regular block structure, the stacking is thick, and no large concave-convex or gully shape appears. As shown in fig. 4, after CO-doping with carbon and oxygen, CO-CN has a more complex porous step-like morphology, the nanosheet layer becomes thinner, gully is obvious, and smoothness is obviously reduced. The modified CO-CN has a larger specific surface area, is beneficial to adsorption of pollutants and provides more active sites, and the stepped shape increases the recombination distance of photon-generated carriers and is beneficial to improving the separation efficiency of the photon-generated carriers on the surface of the photocatalyst.
4. XPS characterization
Using X-ray photoelectron spectrometer (XPS) to g-C 3 N 4 And the elemental composition, valence state and surface functional group of CO-CN before and after use were analyzed. The results are shown in FIGS. 5 to 8.
As can be seen in FIG. 5, g-C 3 N 4 And the CO-CN before and after use has obvious binding energy peaks at 287.2eV, 399.1eV and 532.6eV, which respectively correspond to C, N and O.
XPS spectra at C1s As shown in FIG. 6, two binding energy peaks at 287.80eV and 284.4eV were observed, corresponding to sp 2 Hybridized C atom (C-C bond) with sp in an aromatic ring 2 Bonded carbon (-N-C ═ N-bond). The C1s peak of the modified CO-CN was slightly red shifted, probably due to carbon-oxygen doping.
The spectrum of N1s is shown in FIG. 7, and has triplet peaks at 398.25eV, 399.18eV and 400.67eV, and a single peak at 404.03eV, which correspond to sp 2 Hybridized N (C-N-C), sp 3 Hybrid N (N- [ C)] 3 ) And an amino functional group (C-NH). The binding energy peak of CO — CN after use is slightly blue-shifted, probably due to the photocatalytic reaction affecting the chemical environment around the element.
The spectrum of O1s is shown in FIG. 8, g-C 3 N 4 And CO — CN has two binding energy peaks at 532.26eV and 531.44eV, wherein the binding energy peak at 531.44eV is due to the C — O bond and the binding energy peak at 532.26eV is due to adsorbed water at the photocatalyst surface. By combining the XPS spectrograms and combining the table 1, the content of the modified C element is obviously reduced, and the content of the N element is increased. The content of O element is increased after the CO-CN is used, and the content of N element is reduced because part of sp in the photocatalyst 2 The hybridized N atom is replaced by O atom.
Table 1: g-C 3 N 4 And carbon, nitrogen and oxygen atoms in CO-CNContent of element
5. UV-vis analysis
To clarify g-C 3 N 4 And the reason for the difference of the photocatalytic activity of CO-CN is that the light absorption performance of the photocatalyst is characterized by adopting ultraviolet-visible diffuse reflection spectrum.
As shown in fig. 9, after doping carbon and oxygen, the light absorption capability of CO — CN is significantly improved, and the light absorption edge is expanded. Compared with g-C 3 N 4 The absorption sidebands of CO-CN in the spectral range are slightly "red-shifted". After carbon and oxygen are doped, the light absorption capacity of CO-CN is stronger, more photo-generated electron and hole pairs can be generated, and probably because the CO-CN has a stepped surface structure and has larger specific surface area.
Experimental example 2
The experimental example is used for explaining a degradation method for degrading antibiotics by PMS, and the organic wastewater is specifically oxytetracycline hydrochloride (OTC) wastewater, and comprises the following steps:
1. 0.02g of each CO-CN prepared in the embodiment of the invention is weighed and respectively added into 100mL of oxytetracycline hydrochloride wastewater with the initial concentration of 40mg/L, and the mixture is magnetically stirred for one hour in a dark place to achieve the balance of adsorption and desorption;
2. adding 10mg of Peroxymonosulfate (PMS) into the oxytetracycline hydrochloride solution, placing a light source right above the oxytetracycline hydrochloride wastewater, keeping the distance between the light source and the liquid level of the oxytetracycline hydrochloride wastewater at 15 cm, turning on the light source (a xenon lamp, 300W, lambda >420nm), and carrying out photocatalytic reaction for 60min under the conditions of magnetic stirring and illumination to finish the degradation of the oxytetracycline hydrochloride wastewater.
Determination of degradation efficiency: in the process of the PMS reaction through photocatalytic activation, the photocatalytic degradation liquid in a 4mL reaction container is taken every 10min, filtered by a 0.22-micron water system filter head, detected by an ultraviolet-visible spectrophotometer instrument, and measured for absorbance at 353nm, and the degradation rate of different catalytic systems to oxytetracycline hydrochloride is obtained through calculation.
1. Comparing the effect of different solvents on OTC degradation:
the degradation effect of CO-CN (B1, B2 and A1) prepared by three solvents of water, absolute ethyl alcohol and dimethyl sulfoxide under a CO-CN/PMS/vis system (vis represents visible light) is shown in figure 10.
After illumination for 75min, the degradation rates of the three photocatalysts on OTC are 60.73%, 63.60% and 65.06% respectively. It can be seen that the solvent in the preparation process has little influence on the photocatalytic performance of the photocatalyst, and in three different solvents, the CO-CN prepared by taking absolute ethyl alcohol as the solvent has relatively good OTC degradation effect, and water and dimethyl sulfoxide have the same time.
2. Comparing the effect of precursor formulation on OTC degradation:
the influence of CO-CN (A1, A2, A3: the mol ratio of ammonium sulfate to melamine is 1: 1, 1.5: 1 and 1: 2) with different ratios of ammonium sulfate and melamine on the photocatalytic performance of the CO-CN is researched. As shown in fig. 11.
When the molar ratio of ammonium sulfate to melamine is 1.5: at 1, the best effect of CO-CN on OTC is higher than that of A1 and A3. This is probably because when the ratio of ammonium sulfate to melamine is higher, the doping of carbonyl groups in the prepared CO-CN is more, and the carbonyl groups can provide more reaction sites for PMS activation, so that PMS generates more active free radicals, thereby improving the degradation rate of OTC. However, in the actual preparation of CO — CN, the ammonium sulfate is easily decomposed at high temperature, which causes a part of the precursor to be volatilized from the crucible of the tube furnace during the calcination process, thereby reducing the yield. Under the experimental conditions, ammonium sulfate: melamine 1.5: the yield of CO-CN at 1 is less than 1: one sixth of 1 when proportioning. Comprehensively considering economic benefit and degradation effect factors, adopting ammonium sulfate: melamine 1: 1 to prepare the photocatalyst.
3. Comparing the effect of photocatalyst dosage on OTC degradation:
under the conditions that the OTC concentration is 40mg/L and the PMS dosage is 0.1g/L, the influence of different CO-CN dosages on OTC degradation is examined, and the result is shown in figure 12.
As can be seen from FIG. 12, when the amount of CO-CN added was increased from 0.2g/L to 0.6g/L, the OTC degradation rate was increased from 65.06% to 76.29%. This is because in a certain concentration range, the increase of the concentration of the photocatalyst increases the number of active sites, so as to generate more active free radicals and increase the contact area of the photocatalyst and the OTC. However, when the amount is excessively increased, the penetration of light is hindered by an excessive amount of the photocatalyst, resulting in a decrease in the rate of OTC degradation.
4. Comparison of the Effect of pH on OTC degradation
When the initial OTC concentration is 40mg/L, the PMS adding amount is 0.1g/L and the catalyst adding amount is 0.2g/L, the influence of the initial pH value on the CO-CN photocatalytic degradation OTC is studied. The pH can affect the effectiveness of photocatalytic degradation of contaminants by acting on the surface characteristics of the catalyst, adsorption and the presence of compounds. The results of the experiment are shown in FIG. 13.
From FIG. 13, it can be seen that the OTC degradation rate under alkaline conditions is higher. When the pH value is 9.3, the degradation rate of the OTC after 75min of reaction can reach 69.10%. The reason is that under the alkaline condition, the C ring in the tetracycline antibiotic is easy to be destroyed to generate an isomer with a lactone structure, and under the coordination of PMS, the alkaline environment has better activation effect on PMS. Thereby generating more SO 4 - H, with OH - Combined to form OH (. SO) 4 - +OH - →SO 4 2- OH) to increase the rate of OTC degradation, so an increase in pH is more favorable to photodegradation of tetracycline antibiotics.
5. Reusability of CO-CN
FIG. 14 is a graph showing the change in the rate of OTC degradation by catalyst A1 after 4 reuses. As can be seen from the figure, when the catalyst is used for the first time, the degradation rate of the catalyst A1 to OTC reaches 65.06% after the reaction is carried out for 75min, and after four cycles, the degradation rate is only reduced by 11.45%, which is 53.61%. This may be due to the adsorption of more OTC or small molecule species on the adsorption sites of the porous structure of the CO — CN photocatalyst, resulting in a reduced chance of contacting the oxidizing agent with the active sites or a reduced binding of OTC to the active sites. In general, CO-CN still keeps higher photocatalytic activity after being repeatedly used for four times, and has good practical application prospect.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of carbon and oxygen co-doped graphite phase carbon nitride is characterized by at least comprising the following steps:
s1, dissolving melamine and ammonium sulfate in a solvent to obtain a precursor mixed solution;
s2, drying the precursor mixed solution to obtain a carbon nitride precursor;
and S3, calcining the carbon nitride precursor to obtain carbon-oxygen co-doped graphite-phase carbon nitride.
2. The method according to claim 1, wherein in S1, the molar ratio of melamine to ammonium sulfate is 0.1-10: 1.
3. the production method according to claim 1, wherein in S1, the solvent is selected from water or an organic solvent selected from an alcohol-based organic solvent or a sulfone-based organic solvent;
preferably, the organic solvent is selected from anhydrous ethanol or dimethyl sulfoxide.
4. The method of claim 1, wherein in S2, the drying method is: heating and drying while stirring;
the stirring speed is 150 r/min-350 r/min;
the heating temperature is 30-90 ℃.
5. The method of claim 1, wherein, in step S3,
the temperature rise rate of the calcination is 2 ℃/min-10 ℃/min;
the calcining temperature is 350-600 ℃;
the calcining time is 2-12 hours.
6. The carbon-oxygen co-doped graphite-phase carbon nitride prepared by the method of any one of claims 1-5.
7. The application of the carbon-oxygen co-doped graphite-phase carbon nitride as a photocatalyst in the degradation of organic wastewater by activating persulfate;
preferably, the mass ratio of the carbon-oxygen co-doped graphite phase carbon nitride to the persulfate is 1: 0.1 to 5;
more preferably, the organic wastewater contains antibiotic pollutants.
8. A method for degrading organic pollutants, characterized by comprising at least the following steps:
s1, adding the carbon-oxygen co-doped graphite-phase carbon nitride of claim 6 into the organic pollutant wastewater to be treated, and stirring under a dark condition;
and S2, adding persulfate, and degrading the organic pollutants under the visible light condition.
9. The degradation method according to claim 8, wherein in S1, the initial concentration of the organic pollutants in the wastewater is 5mg/L to 50 mg/L;
the pH value of the wastewater is 7-14;
the concentration of the carbon-oxygen co-doped graphite-phase carbon nitride in the organic pollutant wastewater is 0.01-0.5 g/L;
the stirring time is 30-90 min;
the stirring speed is 150-350 r/min.
10. The degradation method according to claim 8, wherein in S2, the concentration of the persulfate in the organic pollutant wastewater is 0.1-2 g/L, and the degradation time is 1-180 min.
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