CN113318764A - Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst - Google Patents
Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- 230000007547 defect Effects 0.000 title claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
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- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 241000070928 Calligonum comosum Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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—
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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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of semiconductor photocatalysts, and particularly relates to nitrogen defect/boron doped tubular carbon nitrideA preparation method and application of the photocatalyst. The method comprises the following steps: placing melamine and phosphoric acid into an autoclave containing deionized water for hydrothermal reaction, washing a product after the reaction by using the deionized water and drying the product in vacuum to obtain a material which is a supermolecule precursor, calcining the material again, and naturally cooling and grinding the material to obtain tubular carbon nitride; tubular carbon nitride and NaBH4Mixing, grinding uniformly, and calcining in a porcelain boat; and washing the calcined product by HCl and distilled water, and drying in vacuum to obtain the nitrogen defect/boron doped tubular carbon nitride photocatalyst which is marked as D-TCN photocatalyst. The synergistic effect of nitrogen defect/boron doping and the tubular structure can effectively promote light capture, accelerate charge transfer, promote the exposure of more active sites, and remarkably enhance the effects of photocatalytic antibiotic degradation and water decomposition hydrogen production activity.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalysts, and particularly relates to a preparation method and application of a nitrogen defect/boron doped tubular carbon nitride photocatalyst.
Background
The solar-driven photocatalytic degradation of water pollutants and the decomposition of water to produce hydrogen are of great significance for solving the environmental and energy problems in China. The key and feasibility of this technology depends to a large extent on the development of inexpensive, environmentally friendly, and efficient semiconductor materials. Among various photocatalysts, polymer carbon nitride (g-C)3N4) As a non-metal semiconductor nanomaterial, special attention has been paid to its simplicity of synthesis, environmental friendliness, and chemical stability. However g-C3N4The whole structure of the compound has limited active sites, low absorbance and poor charge separation and transfer efficiency, so that the photocatalytic degradation and water decomposition hydrogen production method is low in efficiency.
Recent studies have shown that pyrolysis of self-assembled supramolecular precursors enables tubular carbon nitrides to be obtained, the particular hollow tubular structure of which confers to the material excellent light scattering power, promotes the electron-directed transfer of the support and increases the specific surface area. However, tubular carbon nitride has insufficient light absorption properties and weak oxidation properties at 600nm or less, and thus a good catalytic effect cannot be obtained.
Disclosure of Invention
The invention aims to provide a nitrogen deficiency aiming at some defects in the prior artA preparation method of trap/boron-doped tubular carbon nitride (D-TCN) is provided, and the photocatalytic performance of the tubular carbon nitride (D-TCN) for photocatalytic degradation of antibiotic wastewater and decomposition of water to produce hydrogen under visible light is examined. In effectively retaining tubular g-C3N4The tubular g-C is optimized by a method which is simple and convenient to operate, low in cost and green and pollution-free while the light scattering capacity is excellent3N4The optical and electronic structure of the composite material reduces the separation potential barrier of electron/hole pairs, enhances the utilization rate of visible light, and improves the performance of photocatalytic degradation of antibiotic wastewater and water decomposition for hydrogen production.
In order to achieve the above object of the invention, the following technical solutions are adopted.
A preparation method of a nitrogen defect/boron doped tubular carbon nitride photocatalyst is characterized by comprising the following steps:
Further, in the step 1, the dosage ratio of melamine, phosphoric acid and deionized water is 3-5 g: 0.5-2 g: 70 mL; the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 8-16 h.
Further, in the step 1, the calcining temperature is 500 ℃, the heating rate is 2.3 ℃/min, and the calcining time is 4 h; the protective gas in the calcining process is nitrogen.
Further, step 2 said tubular carbon nitride and NaBH4The mass ratio of (1): (0.06-0.8).
Further, when the porcelain boat is calcined in the tube furnace in the step 2, the porcelain boat is calcined with a cover, and a semi-closed state is kept.
Further, in the step 2, the calcining temperature is 450 ℃, the heating rate is 2.3 ℃/min, and the calcining time is 0.5 h; the protective gas in the calcining process is nitrogen.
Further, the concentration of HCl in the step 2 is 0.5-2 mol/L.
Further, in the step 2, the drying temperature is 50-70 ℃, and the time is 12-24 hours.
The invention also provides application of the D-TCN photocatalyst in photocatalytic degradation of antibiotics and decomposition of water to produce hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a D-TCN photocatalyst, and the synergistic effect of nitrogen defect/boron doping and a tubular structure can effectively promote light capture, accelerate charge transfer and promote the exposure of more active sites. Meanwhile, cyano (nitrogen defect) and boron dopant are fused into the framework of the tubular carbon nitride to promote the absorption of oxygen, form superoxide radical and deepen valence band position to improve the photocatalytic oxidation performance.
2. The invention firstly proposes that based on a supermolecule self-assembly method, NaBH is used4Strategy optimization of tubular g-C by thermal reduction method3N4(TCN) optical and electronic structure, lowering electron/hole pair separation barrier and promoting more active site exposure, thereby improving its photocatalytic performance. Compared with the traditional g-C photocatalyst, the D-TCN photocatalyst provided by the invention3N4Has remarkably enhanced photocatalytic antibiotic wastewater degradation and water decomposition hydrogen production activity, and g-C3N4Has a large interlayer distance and rich functional groups (e.g., -NH)2and-OH) to make it easier to introduce defects/dopants into the tubular structure, the synthesized photocatalyst is green and pollution-free, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the D-TCN photocatalyst prepared in example 1;
FIG. 2 is a graph showing g-C prepared in comparative examples 1-23N4The X-ray diffraction patterns of TCN and the D-TCN photocatalyst prepared in example 1;
FIG. 3 is a graph of g-C prepared in comparative examples 1-23N4Transmission electron microscopy images of TCN and the D-TCN photocatalyst prepared in example 1;
FIG. 4 is a graph of g-C prepared in comparative examples 1-23N4The Fourier-Infrared transform Spectroscopy of TCN and the D-TCN photocatalyst prepared in example 1;
FIG. 5 is a graph of g-C prepared in comparative examples 1-23N4TCN and the UV-Vis diffuse reflectance spectra of the D-TCN photocatalyst prepared in example 1;
FIG. 6 is a graph of g-C prepared in comparative examples 1-23N4The photoluminescence spectra of TCN and the D-TCN photocatalyst prepared in example 1;
FIG. 7 is a graph of g-C prepared in comparative examples 1-23N4TCN and D-TCN photocatalyst prepared in example 1 under visible light (. lamda.)>420nm) of the photocatalytic degradation rate of TC wastewater;
FIG. 8 is a graph of the rate of catalytic degradation of TC wastewater for four cycles of the D-TCN photocatalyst prepared in example 1 under visible light (λ >420 nm).
FIG. 9 is a graph of the rate of hydrogen production by water decomposition of the D-TCN photocatalyst prepared in example 1 under visible light (λ >420 nm).
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. However, it should not be construed as limiting the invention. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Comparative example 1:
g-C3N4preparation of the photocatalyst:
weighing 5g of melamine in a crucible, covering the crucible cover, keeping the crucible in a semi-closed state, placing the crucible in a muffle furnace, heating to 500 ℃ at a heating rate of 2.3 ℃/min, calcining for 4h, and naturally cooling to room temperature after calcining is finished to obtain g-C3N4。
Comparative example 2:
preparation of TCN photocatalyst:
4g of melamine and 1g of phosphoric acid are weighed into 70mL of deionized water and stirred vigorously for 0.5 h. The solution was then transferred to a 100mL autoclave and reacted at 180 ℃ for 12 h. The generated supramolecular precursor was washed with deionized water until phosphoric acid was completely washed, and then dried at 60 ℃. And finally, heating the obtained supermolecule precursor to 500 ℃ in a muffle furnace at the heating rate of 2.3 ℃/min, and calcining for 4h to obtain the TCN.
Example 1:
(1) preparation of TCN photocatalyst:
weighing 3g of melamine and 0.5g of phosphoric acid, adding into 70mL of deionized water, and intensively stirring for 0.5 h; then transferring the solution into a 100mL autoclave, and reacting for 8h at 190 ℃; the generated supramolecular precursor was washed with deionized water until phosphoric acid was completely washed, and then dried at 60 ℃. Finally, heating the obtained supermolecule precursor to 500 ℃ in a muffle furnace at the heating rate of 2.3 ℃/min, and calcining for 4h to obtain TCN;
(2) preparation of D-TCN photocatalyst:
0.2g of TCN and 160mg of NaBH4Mixing and grinding uniformly, placing the mixture in a corundum porcelain boat, covering a porcelain boat cover, keeping the porcelain boat in a semi-closed state, placing the mixture in a tube furnace, heating to 450 ℃ at the heating rate of 2.3 ℃/min under the nitrogen atmosphere, at the heating rate of 2.3 ℃/min, calcining for 0.5h, naturally cooling to room temperature after the calcination is finished, washing with HCl (0.5mol/L) and water twice, then placing the mixture in a vacuum drying box, and drying at 50 ℃ to obtain the D-TCN.
Example 2:
(1) preparation of TCN photocatalyst:
weighing 4g of melamine and 1g of phosphoric acid, adding into 70mL of deionized water, and intensively stirring for 0.5 h; then transferring the solution into a 100mL autoclave, and reacting for 12h at 200 ℃; the generated supramolecular precursor was washed with deionized water until phosphoric acid was completely washed, and then dried at 60 ℃. Finally, heating the obtained supermolecule precursor to 500 ℃ in a muffle furnace at the heating rate of 2.3 ℃/min, and calcining for 4h to obtain TCN;
(2) preparation of D-TCN photocatalyst:
0.4g of TCN and 80mg of NaBH4Mixing and grinding uniformly, placing the mixture in a corundum porcelain boat, covering a porcelain boat cover, keeping the porcelain boat in a semi-closed state, placing the mixture in a tube furnace, heating to 450 ℃ at the heating rate of 2.3 ℃/min under the nitrogen atmosphere, heating at the heating rate of 2.3 ℃/min, calcining for 0.5h, naturally cooling to room temperature after the calcination is finished, washing with HCl (1mol/L) and water twice, then placing the mixture in a vacuum drying box, and drying at the temperature of 60 ℃ to obtain the D-TCN.
Example 3:
(1) preparation of TCN photocatalyst:
weighing 5g of melamine and 2g of phosphoric acid, adding the melamine and the phosphoric acid into 70mL of deionized water, and intensively stirring for 0.5 h; then transferring the solution into a 100mL autoclave, and reacting for 10h at 180 ℃; washing the generated supramolecular precursor with deionized water until phosphoric acid is completely washed, and then drying at 60 ℃; finally, heating the obtained supermolecule precursor to 500 ℃ in a muffle furnace at the heating rate of 2.3 ℃/min, and calcining for 4h to obtain TCN;
(2) preparation of D-TCN photocatalyst:
0.6g of TCN and 40mg of NaBH4Mixing and grinding uniformly, placing the mixture in a corundum porcelain boat, covering a porcelain boat cover, keeping the porcelain boat in a semi-closed state, placing the mixture in a tube furnace, heating to 450 ℃ at the heating rate of 2.3 ℃/min under the nitrogen atmosphere, at the heating rate of 2.3 ℃/min, for 0.5h, naturally cooling to room temperature after calcination, washing with HCl (2mol/L) and water twice, then placing the mixture in a vacuum drying oven, and drying at 70 ℃ to obtain the D-TCN.
Subsequent performance tests were carried out with the D-TCN prepared in example 1:
experimental process for photocatalytic degradation of tetracycline hydrochloride (TC):
0.025g of the photocatalyst powder D-TCN prepared in example 1 was weighed out and added to a solution containing 50mL of TC at a TC concentration of 10 mg/L. Before the photoreaction, the mixture was stirred in the dark for 1 hour to reach the adsorption-desorption equilibrium. Then, the photoreaction was performed while maintaining the temperature at room temperature. After the light source was turned on, 3mL of the solution was taken at given time intervals, and after filtering the photocatalyst powder with a 0.45 μm microporous filter, the absorbance of TC was measured at 357nm by an ultraviolet-visible spectrophotometer.
The experimental process of photocatalytic water splitting hydrogen production:
0.025g of the prepared photocatalyst powder was weighed into an aqueous solution (25mL) containing 10 vol.% triethanolamine and 3 wt.% Pt and sonicated for 30min to disperse uniformly. Prior to the reaction, the reactor was degassed by pulling a vacuum to remove air dissolved in water. The temperature of the reactor was maintained at 6 ℃ by the fluidity of the cooling circulation water. Irradiation with a 300W xenon stabilized light source equipped with a 420nm cut-off filter, with N2As carrier gas, a thermal conductivity detector and
the molecular sieve column was used for on-line gas chromatography analysis of the liberated hydrogen.
FIG. 1 is a scheme for the synthesis of D-TCN. As can be seen, D-TCN is prepared by a two-step method of hydrolytic self-assembly and high-temperature roasting.
FIG. 2 shows g-C3N4X-ray diffraction patterns of TCN and D-TCN. The crystal structure of the prepared photocatalyst is shown, and all samples have two distinct diffraction peaks. In the XRD pattern of FIG. 2, g-C3N4The (002) crystal plane at 27.3 deg., of the samples TCN and D-TCN had a strong diffraction peak corresponding to the stacking structure from layer to layer of the samples. The peak of the D-TCN sample corresponding to the (100) crystal plane at 13.1 ℃ is reduced, indicating that NaBH4And g-C3N4The reaction results in loss of ordered structure in the framework, destroying some of the in-plane repeating heptazine building blocks.
FIGS. 3(a), (b) and (C) are g-C, respectively3N4Transmission electron micrographs of TCN and D-TCN, and it can be seen that g-C3N4Is an irregular block structure. The TCN is a hollow tube with the tubular diameter of 1-2 mu m, and visual evidence is provided for revealing the morphology of the TCN photocatalyst. As can be observed in the D-TCN plot of FIG. 3(c), addition of NaBH4And then, the shape of the D-TCN is still a hollow tubular structure, and the diameter of the tubular structure is similar to that of the TCN, which shows that the structure can still keep the integrity of the framework at the high temperature of 450 ℃.
FIG. 4 shows g-C3N4And Fourier transform infrared spectrograms of TCN and D-TCN, and the molecular structure of the prepared photocatalyst is analyzed. All samples were at 810cm-1The absorption peak at (A) is due to the breathing pattern of the s-triazine ring and lies between 1200 and 1700cm-1The absorption within the domain is due to the stretching mode of the CN heterocycle. Furthermore, 3150 to 3600cm-1A broad band within the range corresponds to N-H and-OH oscillations; it was clearly observed that upon addition of NaBH4In the D-TCN sample, the D-TCN is 3150 to 3600cm-1The intensity of the N-H vibration peak between the two gradually decreases, and a peak at 2182cm appears-1The new peak at (A) corresponds to the cyano (N.ident.C-) asymmetric tensile vibration. These results indicate that NaBH4And g-C3N4By thermal reaction of (C) to reduce-NH2Concentration of groups and introduction of N.ident.C-groups into the D-TCN sample, such that the D-TCN acquires nitrogen deficiency (i.e.introduced N.ident.C-).
FIG. 5 is g-C3N4TCN and D-TCN. As can be seen from FIG. 5, g-C3N4Shows a visible absorption edge at 450 nm; and g-C3N4Compared with TCN, the absorption edge of the D-TCN sample shows obvious red shift, and the corresponding band gap is also obviously reduced; the red shift phenomenon is caused by the uniform distribution of boron doping and nitrogen defects in the D-TCN sample, and shows that the tubular structure of the D-TCN makes the doping and the defects more uniform; and defects and doping broaden the visible light absorption capability of the photocatalytic material.
FIG. 6 shows g-C3N4TCN and D-TCN photoluminescence spectra. It can be seen that g-C3N4The photoluminescence spectrum peak position of (A) is about 460nm, the peak intensity is higher, and the peak intensity of TCN is obviously reduced. The low peak intensity of the photoluminescence spectrum represents a low electron hole recombination rate. After introducing boron doping and nitrogen defects, the peak intensity of the D-TCN sample is sharply reduced, and the weakened peak intensity proves that doping and defects enable electron/hole of the catalystThe recombination rate is lower.
FIG. 7 is g-C3N4Graph of photocatalytic degradation rate of TCN and D-TCN to TC (tetracycline) wastewater under visible light. As shown in FIG. 7, g-C was observed within 80min of visible light irradiation3N4The degradation reaction is slow, and the degradation rate only reaches 19.5 percent. In contrast, the degradation performance of D-TCN is remarkably improved, the degradation rate of TC reaches 68.2%, and the improvement of the D-TCN performance is attributed to the improvement of charge separation efficiency, the increase of specific surface area and proper energy band structure.
FIG. 8 shows the stability test of D-TCN. 4 times of cyclic degradation experiments are carried out on the D-TCN photocatalyst so as to investigate the stability and reusability of the D-TCN photocatalyst; after 4 cycles of continuous operation, the degradation activity of the D-TCN is not obviously changed, and the high photocatalytic performance is still maintained, which indicates that the D-TCN is a stable photocatalyst and can be circularly used for TC wastewater treatment.
FIG. 9 shows g-C3N4And the rate chart of the hydrogen production by water decomposition of TCN and D-TCN under visible light. As can be seen from the figure, g-C3N4The photocatalytic hydrogen production rate is low, and the average hydrogen production rate is 186.3 mu mol h-1g-1. In contrast, the D-TCN has higher hydrogen production capacity, and the average hydrogen production rate is 789.2 mu mol h-1g-1Are each g-C3N4And 4.2 times and 1.7 times TCN. Albeit g-C3N4And TCN have deeper conduction band positions, but the improvement of charge transfer and separation efficiency, the increase of specific surface area and better light absorption of D-TCN make it more than g-C3N4And TCN has higher photocatalytic hydrogen production activity. Therefore, the D-TCN photocatalyst can be used as a high-efficiency photocatalyst for producing hydrogen and degrading TC.
It should be noted that the above-described embodiments may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Thus, it will be appreciated by those skilled in the art that the invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.
Claims (9)
1. A preparation method of a nitrogen defect/boron doped tubular carbon nitride photocatalyst is characterized by comprising the following steps:
step 1, putting melamine and phosphoric acid into an autoclave containing deionized water for hydrothermal reaction, washing a product after the reaction is finished by the deionized water and drying the product in vacuum to obtain a supramolecular precursor; calcining the obtained supermolecule precursor in a tube furnace, and naturally cooling and grinding to obtain tubular carbon nitride, which is marked as TCN;
step 2, tubular carbon nitride and NaBH obtained in step 14After mixing and grinding uniformly, putting the mixture into a porcelain boat and calcining the mixture in a tube furnace; and washing the calcined product by HCl and distilled water, and then drying in vacuum to obtain the nitrogen defect/boron doped tubular carbon nitride photocatalyst which is marked as a D-TCN photocatalyst.
2. The method for preparing the nitrogen defect/boron doped tubular carbon nitride photocatalyst according to claim 1, wherein the dosage ratio of the melamine, the phosphoric acid and the deionized water in the step 1 is 3-5 g: 0.5-2 g: 70 mL; the temperature of the hydrothermal reaction is 180-200 ℃, and the time is 8-16 h.
3. The method for preparing a nitrogen defect/boron doped tubular carbon nitride photocatalyst as claimed in claim 1, wherein the calcination temperature in step 1 is 500 ℃, the temperature rise rate is 2.3 ℃/min, and the calcination time is 4 h; the protective gas in the calcining process is nitrogen.
4. The method of claim 1, wherein the step 2 comprises forming a tubular layer of carbon nitride and NaBH, and wherein the tubular layer of carbon nitride and NaBH is formed by a process comprising4The mass ratio of (1): (0.06-0.8).
5. The method of claim 1, wherein the porcelain boat is calcined in a tube furnace in step 2, and the porcelain boat is calcined with a cover and kept in a semi-closed state.
6. The method for preparing a nitrogen defect/boron doped tubular carbon nitride photocatalyst as claimed in claim 1, wherein the calcination temperature in step 2 is 450 ℃, the temperature rise rate is 2.3 ℃/min, and the calcination time is 0.5 h; the protective gas in the calcining process is nitrogen.
7. The method for preparing a nitrogen defect/boron doped tubular carbon nitride photocatalyst according to claim 1, wherein the concentration of HCl in the step 2 is 0.5-2 mol/L.
8. The method for preparing the nitrogen defect/boron doped tubular carbon nitride photocatalyst according to claim 1, wherein the drying temperature in the step 2 is 50-70 ℃ and the drying time is 12-24 h.
9. Use of the nitrogen defect/boron doped tubular carbon nitride photocatalyst prepared according to any one of claims 1 to 8 in the photocatalytic condition for degrading antibiotics and decomposing water to produce hydrogen.
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