CN112958139A - Preparation of CNK-OH/ferroferric oxide composite material and application of CNK-OH/ferroferric oxide composite material in photocatalytic degradation of tetracycline hydrochloride - Google Patents
Preparation of CNK-OH/ferroferric oxide composite material and application of CNK-OH/ferroferric oxide composite material in photocatalytic degradation of tetracycline hydrochloride Download PDFInfo
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- CN112958139A CN112958139A CN202110252058.5A CN202110252058A CN112958139A CN 112958139 A CN112958139 A CN 112958139A CN 202110252058 A CN202110252058 A CN 202110252058A CN 112958139 A CN112958139 A CN 112958139A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 title claims abstract description 35
- 229960004989 tetracycline hydrochloride Drugs 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
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- 229940088710 antibiotic agent Drugs 0.000 description 2
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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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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 preparation method of a CNK-OH/ferroferric oxide composite material and application of the CNK-OH/ferroferric oxide composite material in photocatalytic degradation of tetracycline hydrochloride. The invention adopts dicyandiamide, KCl and NaOH as raw materials to synthesize a precursor CNK-OH by a solid-state thermal polycondensation method, and then Fe is subjected to impregnation3O4Loading on CNK-OH to obtain CNK-OH/Fe3O4A composite material. The composite material can be used as a photocatalyst for photocatalytic degradation of tetracycline hydrochloride, separation and transfer of photon-generated carriers are optimized through K implantation and hydroxyl modification, and improvement of dynamic behavior is realized. Despite Fe3O4Does not affect the transfer of photo-carriers in the volume, but it promotes the utilization of photoelectrons on the surface of the catalyst. Thus, implantation of K, hydroxyl modification andFe3O4the load constructs a rapid transfer and conversion channel for a photon-generated carrier, which is beneficial to more effectively conveying photoelectrons to the surface of the photocatalyst and generating active free radicals, so that CNK-OH/Fe3O4The photocatalytic activity is obviously improved.
Description
Technical Field
The invention belongs to the technical field of environmental materials, and particularly relates to a preparation method of a CNK-OH/ferroferric oxide composite material.
Background
Currently, with the rapid development of social economy, environmental problems have been raised as the focus of wide attention, and the threat to human health and social life is immeasurable, so that the progress of ecological civilization construction and sustainable development is seriously hindered, and the environmental problems can not be ignored before raining. Tetracycline hydrochloride (TCHC) is a broad spectrum antibacterial agent that has been widely used to treat diseases in humans and many animals. Since only 30% of TCHC is absorbed by the organism, the remainder enters the environment through urine and feces, and naturally accumulates in various bodies of water. In addition, the residues of TCHCs lead to the production of antibiotic-resistant pathogens and to the transfer of antibiotic-resistant genes, posing a serious threat to human health and ecological safety. Therefore, the removal of TC from the environment has become an urgent problem to be solved. Currently, there are several treatments for antibiotics in water, such as biological, physical and chemical methods. However, the method has fatal weaknesses in the degradation process, such as high energy consumption, low efficiency, secondary pollution and the like. The photocatalytic technology has high degradation rate, small secondary pollution and easy treatment, and nearly all antibiotics in sewage treatment can be degraded. The photocatalytic technology is a novel technology that converts light energy into chemical energy, and then generates holes, hydroxyl radicals, and superoxide radicals to degrade contaminants. It is considered one of the most effective methods for degrading pollutants due to its superior sustainable energy characteristics, avoidance of secondary pollution, economic cost and convenience of operation, and thus has attracted extensive attention.
How to efficiently utilize solar energy to improve photocatalytic degradation efficiency has become a topic of hot research. In the reported photocatalytic materials, g-C3N4(CN) based material as a novel Metalfree polymerThe photocatalyst has good photocatalytic performance under the irradiation of visible light, and the photocatalyst is low in cost, non-toxic and stable in heat. Thus, g-C3N4(CN) has been widely used for the degradation of organic pollutants and the direct production of clean hydrogen. However, g-C3N4The (CN) has a light absorption edge of about 450nm and a band gap of 2.7eV, and the use of the (CN) under the irradiation of visible light is limited. Therefore, there is a need to develop an effective visible light responsive photocatalyst to extend its spectral response to higher absorption wavelengths. In the research of the invention, the CNK-OH/Fe for efficiently degrading tetracycline hydrochloride under visible light is provided3O4A photocatalyst.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a preparation method of a CNK-OH/ferroferric oxide composite material with visible light response;
the invention also aims to provide a CNK-OH/ferroferric oxide composite material used as a photocatalyst for photocatalytic degradation of tetracycline hydrochloride.
Mono, CNK-OH/Fe3O4Preparation of composite materials
(1) Preparation of CNK-OH: the dicyandiamide, KCl and NaOH are ground and fully mixed, the mixture is heated to 300-600 ℃ (preferably 510-570 ℃) at the heating rate of 1-20 ℃/min (preferably 2.3 ℃/min) in a muffle furnace, the mixture is roasted at the constant temperature for 0.1-10 h (preferably 2-4), distilled water is added to dissolve the obtained polymer, and then the mixture is subjected to ultrasonic treatment, centrifugation, washing and vacuum drying at the temperature of 60-80 ℃ for 12-24 h to obtain a precursor, wherein the precursor is marked as CNK-OH. Wherein the molar ratio of dicyandiamide to KCl to NaOH is 7:4: 1; the ultrasonic treatment is intermittent ultrasonic treatment at 20000-25000 Hz for 0.5-1 h and 3-5 h, and the intermittent ultrasonic treatment is to regulate and control the appearance of the polymer in the dissolving process.
（2）CNK-OH/Fe3O4Preparing a composite material: dispersing CNK-OH in distilled water to obtain CNK-OH dispersion, adding FeCl3•6H2O and FeCl2•4H2Stirring O, mixing, adding NH3•H2Stirring and reacting O at 60-90 ℃ for 30-60 min, collecting the product by using a magnet, washing the product by using ethanol, and performing vacuum drying at 60-80 ℃ for 12-24 h to finally obtain K implantation, hydroxyl modification and Fe3O4Supported composite, labelled CNK-OH/Fe3O4. Wherein, CNK-OH and FeCl3•6H2The mass ratio of O is 1: 0.027-1: 0.162; CNK-OH and FeCl2•4H2The mass ratio of O is 0.01-0.06; FeCl3•6H2O and FeCl2•4H2The molar ratio of O is 2: 1; CNK-OH and NH3•H2The mass-to-volume ratio of O is 0.15-1 g/mL.
Di, CNK-OH/Fe3O4Characterization of the composite Material
1. UV-vis absorption Spectroscopy
FIG. 1 shows CNK-OH and 5% CNK-OH/Fe3O4(5% represents CNK-OH/Fe)3O4Middle Fe3O4Content of 5%) composite material, the absorption edge of pure CNK-OH is about 480nm, and CNK-OH/Fe is compared with pure CNK-OH3O4The composite material has an absorption edge with longer wavelength, the wavelength is obviously red-shifted to show that the band gap energy is reduced, and the composite material can absorb more visible light, which indicates that Fe3O4Has strong influence on the optical performance of the synthetic CNK-OH group catalyst and shows better photocatalytic performance.
2. Fourier transform infrared spectrogram (FT-IR)
FIG. 2 shows CNK-OH and different Fe3O4CNK-OH/Fe at content3O4For the determination of hydroxyl groups on the sample, fourier transform infrared spectroscopy (FT-IR) was used. In the spectrum of CNK-OH, 1147, 2142 and 2177cm-1The appearance of 3 peaks indicates that the hydroxyl groups are stably grafted on the CNK when KCl is introduced. CNK-OH loaded Fe3O4These latter peaks remained unchanged, indicating that CNK-OH is loaded with Fe3O4The post hydroxyl group can still exist stably. At 1200--1The series of peaks in the range, attributable to stretching vibrations of the CN heterocycle, was at 808cm-1The sharp peak at (A) is the bending vibration of the heptazine ring, indicating g-C3N4Is composed of heptazine monomers.
III, CNK-OH/Fe3O4Photocatalytic degradation of composite materials
The photocatalytic degradation performance of tetracycline hydrochloride was quantitatively analyzed using a UV-2500 UV-visible spectrophotometer. A300W Xe lamp (Aulight, CEL-HXF 300) was used as the illumination source. 20mg of CNK-OH/Fe3O4The photocatalyst is dissolved in 50ml of tetracycline hydrochloride (TCHC) aqueous solution, and the pH is adjusted to 3-4. Reacting the suspension for 1h under stirring in a dark environment to reach the adsorption-desorption balance of the catalyst, and sampling every 30min during the reaction; the suspension was irradiated with visible light (300W Xe lamp (Aulight, CEL-HXF 300)) and gassed (air, N, respectively)2（N2As reference), O2) Sampling at certain time intervals, collecting separated supernatant, and performing quantitative analysis by using an ultraviolet-visible spectrophotometer.
FIG. 3 shows CNK-OH and Fe3O4And CNK-OH/Fe3O4The photocatalytic degradation performance diagram for degrading tetracycline hydrochloride. FIG. 3a shows the degradation of tetracycline hydrochloride by CNK-OH under different gas conditions. From FIG. 3a, it can be easily seen that CNK-OH is in air, O under visible light irradiation2The degradation rate of tetracycline hydrochloride in 120min under the condition is 49 percent and 51 percent respectively. In FIG. 3b, it can be seen that the light is also visible and air, O, is introduced2In the case of (1), Fe3O4The degradation rate of tetracycline hydrochloride in 120min is 50% and 53% respectively. As can be seen in FIG. 3c, CNK-OH/Fe under visible light irradiation3O4In the air, O2The degradation of tetracycline hydrochloride in 120min in the system can reach 88.5 percent and 92.5 percent. CNK-OH/Fe3O4In a visible light and oxygen system, the degradation of the tetracycline hydrochloride is obviously improved because a synergistic effect exists between the light Fenton reaction and the in-situ catalytic degradation, namely, the oxygen-related free radicals participate in the light degradation reaction, and then the tetracycline hydrochloride is degraded through light catalysis. FIG. 3d shows the CNK-OH/Fe ratios in the visible light irradiation without gas introduction into the gas system3O4Degradation rate of tetracycline hydrochloride. Apparently, 5% CNK-OH/Fe3O4Has the best degradation effect on tetracycline hydrochloride.
In conclusion, the invention adopts dicyandiamide, KCl and NaOH as raw materials to synthesize the precursor CNK-OH by a solid-state thermal polycondensation method, and Fe is subjected to impregnation method3O4Loaded on CNK-OH to obtain K implanted and hydroxyl modified composite material CNK-OH/Fe3O4. The composite material can be used as a photocatalyst for photocatalytic degradation of tetracycline hydrochloride, separation and transfer of photon-generated carriers are optimized through K implantation and hydroxyl modification, and improvement of dynamic behavior is realized. Despite Fe3O4Does not affect the transfer of photo-carriers in the volume, but it promotes the utilization of photoelectrons on the surface of the catalyst. Thus, K implantation, hydroxyl modification and Fe3O4The load constructs a rapid transfer and conversion channel for a photon-generated carrier, which is beneficial to more effectively conveying photoelectrons to the surface of the photocatalyst and generating active free radicals, so that CNK-OH/Fe3O4The photocatalytic activity is obviously improved.
Drawings
FIG. 1 shows CNK-OH and CNK-OH/Fe3O4Ultraviolet and visible absorption spectrum of (1).
FIG. 2 shows CNK-OH and CNK-OH/Fe3O4An infrared spectrum of (1).
FIG. 3 shows CNK-OH and Fe3O4And CNK-OH/Fe3O4The photocatalytic degradation performance of (1).
Detailed Description
The following is a description of the present invention by way of specific embodiments3O4The preparation method and photocatalytic degradation performance of the composite material are further explained.
Example 1
(1) Preparation of CNK-OH: dicyandiamide (more than or equal to 99.0 percent), KCl (more than or equal to 99.5 percent) and NaOH (98.0 percent) are ground and fully mixed (the molar ratio of dicyandiamide to KCl to NaOH is 7:4: 1), the mixture is heated to 550 ℃ in a muffle furnace at the speed of 2.3 ℃/min, the mixture is calcined at constant temperature for 2-4 h, after the temperature is reduced, a polymer is taken out, distilled water is added to dissolve the polymer to prepare a solution of 1 g/L, and then the solution is subjected to ultrasonic treatment, centrifugation at 8000-10000 r/min for 3-5 min, washing and vacuum drying at 80 ℃ for 24h to obtain a precursor, wherein the precursor is marked as CNK-OH.
（2）CNK-OH/Fe3O4Preparing a composite material: dispersing 1g CNK-OH in 20mL distilled water to obtain CNK-OH suspension, adding FeCl3•6H2O (0.1mmol, 0.027g) and FeCl2•4H2O (0.05mmol, 0.010g), stirred at 80 ℃ for 30min, then 1ml NH3•H2Rapidly injecting O into the mixture, stirring at 80 deg.C for 30min, collecting the product with magnet, washing with ethanol for several times, drying in vacuum drying oven, cooling, and collecting the sample to obtain K implant, hydroxyl modification and Fe3O4Supported composite, labelled CNK-OH/Fe3O4。
（3）CNK-OH/Fe3O4The performance of the tetracycline hydrochloride photocatalytic degradation is as follows: under visible light irradiation, CNK-OH/Fe3O4The degradation rate of tetracycline hydrochloride in 120min reaches 75 percent; CNK-OH/Fe3O4At O2The degradation rate of tetracycline hydrochloride in the system within 120min reaches 92.5 percent, and the degradation efficiency is highest.
Example 2
(1) Preparation of CNK-OH: the same as in example 1.
（2）CNK-OH/Fe3O4Preparing a composite material: dispersing 1g CNK-OH in 20mL distilled water to obtain CNK-OH suspension, adding FeCl3•6H2O (0.2mmol, 0.054g) and FeCl2•4H2O (0.1mmol, 0.020g), stirred at 80 ℃ for 30min, then 2ml NH3•H2Rapidly injecting O into the mixture, stirring at 80 deg.C for 30min, collecting the product with magnet, washing with ethanol for several times, drying in vacuum drying oven, cooling, and collecting the sample to obtain K implant, hydroxyl modification and Fe3O4Supported composite, labelled CNK-OH/Fe3O4。
（3）CNK-OH/Fe3O4The performance of the tetracycline hydrochloride photocatalytic degradation is as follows: in the visibleUnder light irradiation, CNK-OH/Fe3O4The degradation rate of tetracycline hydrochloride in 120min reaches 70.5 percent; CNK-OH/Fe3O4At O2The degradation rate of tetracycline hydrochloride in the system within 120min reaches 85 percent.
Example 3
(1) Preparation of CNK-OH: the same as in example 1.
（2）CNK-OH/Fe3O4Preparing a composite material: dispersing 1g CNK-OH in 20mL distilled water to obtain CNK-OH suspension, adding FeCl3•6H2O (0.4mmol, 0.108g) and FeCl2•4H2O (0.2mmol, 0.040g), stirred at 80 ℃ for 30min, then 4ml NH3•H2Rapidly injecting O into the mixture, stirring at 80 deg.C for 30min, collecting the product with magnet, washing with ethanol for several times, drying in vacuum drying oven, cooling, and collecting the sample to obtain K implant, hydroxyl modification and Fe3O4Supported composite, labelled CNK-OH/Fe3O4。
（3）CNK-OH/Fe3O4The performance of the tetracycline hydrochloride photocatalytic degradation is as follows: under visible light irradiation, CNK-OH/Fe3O4The degradation rate of tetracycline hydrochloride in 120min reaches 70 percent; CNK-OH/Fe3O4At O2The degradation rate of tetracycline hydrochloride in the system within 120min reaches 78.5 percent.
Example 4
(1) Preparation of CNK-OH: the same as in example 1.
（2）CNK-OH/Fe3O4Preparing a composite material: dispersing 1g CNK-OH in 20mL distilled water to obtain CNK-OH suspension, adding FeCl3•6H2O (0.6mmol, 0.162g) and FeCl2•4H2O (0.3mmol, 0.060g), stirred at 80 ℃ for 30min, then 6ml NH3•H2Rapidly injecting O into the mixture, stirring at 80 deg.C for 30min, collecting the product with magnet, washing with ethanol for several times, drying in vacuum drying oven, cooling, and collecting the sample to obtain K implant, hydroxyl modification and Fe3O4Supported composite, markingIs CNK-OH/Fe3O4。
（3）CNK-OH/Fe3O4The performance of the tetracycline hydrochloride photocatalytic degradation is as follows: under visible light irradiation, CNK-OH/Fe3O4The degradation rate of tetracycline hydrochloride in an air system within 120min reaches 63.5 percent; CNK-OH/Fe3O4At O2The degradation rate of tetracycline hydrochloride in the system within 120min reaches 73%.
Claims (8)
1. A preparation method of a CNK-OH/ferroferric oxide composite material comprises the following steps:
(1) preparation of CNK-OH: grinding and fully mixing dicyandiamide, KCl and NaOH, heating to 300-600 ℃ in a muffle furnace at the heating rate of 1-20 ℃/min, roasting at constant temperature for 0.1-10 h, adding distilled water to dissolve the obtained polymer, and then performing ultrasonic treatment, centrifugation, washing and vacuum drying to obtain a precursor, wherein the label is CNK-OH;
（2）CNK-OH/Fe3O4preparing a composite material: dispersing CNK-OH in distilled water to obtain dispersion, adding FeCl3•6H2O and FeCl2•4H2O is fully stirred and mixed evenly, and NH is added3•H2Stirring and reacting O at 60-90 ℃ for 30-60 min, collecting the product with a magnet, washing with ethanol, and drying in vacuum to obtain CNK-OH/Fe3O4A composite material.
2. The preparation method of the CNK-OH/ferroferric oxide composite material as claimed in claim 1, wherein the CNK-OH/ferroferric oxide composite material comprises the following steps: in the step (1), the molar ratio of dicyandiamide to KCl to NaOH is 7:4: 1.
3. The preparation method of the CNK-OH/ferroferric oxide composite material as claimed in claim 1, wherein the CNK-OH/ferroferric oxide composite material comprises the following steps: in the step (1), the ultrasound is interrupted at 20000-25000 Hz for 0.5-1 h, and the ultrasound lasts for 3-5 h.
4. The method for preparing CNK-OH/ferroferric oxide composite material according to claim 1, wherein the CNK-OH/ferroferric oxide composite material is prepared by a method comprising the steps of: in step (2), CNK-OH and FeCl3•6H2The mass ratio of O is 1: 0.027-1: 0.162; CNK-OH and FeCl2•4H2The mass ratio of O is 0.01-0.06.
5. The preparation method of the CNK-OH/ferroferric oxide composite material as claimed in claim 1, wherein the CNK-OH/ferroferric oxide composite material comprises the following steps: in step (2), FeCl3•6H2O and FeCl2•4H2The molar ratio of O is 2: 1.
6. The preparation method of the CNK-OH/ferroferric oxide composite material as claimed in claim 1, wherein the CNK-OH/ferroferric oxide composite material comprises the following steps: in step (2), CNK-OH and NH3•H2The mass-to-volume ratio of O is 0.15-1 g/mL.
7. The preparation method of the CNK-OH/ferroferric oxide composite material as claimed in claim 1, wherein the CNK-OH/ferroferric oxide composite material comprises the following steps: in the steps (1) and (2), the vacuum drying is carried out for 12-24 hours at a constant temperature of 60-80 ℃.
8. The CNK-OH/ferroferric oxide composite material prepared by the method of claim 1 is used as a photocatalyst for photocatalytic degradation of tetracycline hydrochloride.
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