CN114904560A - Preparation method and application of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye - Google Patents
Preparation method and application of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 132
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 11
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- 230000002950 deficient Effects 0.000 claims abstract description 43
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
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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
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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
- B01J37/16—Reducing
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/36—Organic compounds containing halogen
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of inorganic functional material preparation, and particularly relates to a preparation method and application of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dyeCarbon-deficient carbon nitride, and then loading the bismuth simple substance on the carbon-deficient carbon nitride by a chemical reduction method. The preparation method of the invention introduces surface defects and metal loading, and the prepared bismuth-loaded carbon-deficient carbon nitride has an active phase g-C for photocatalytic degradation of rhodamine B 3 N 4 There is a great improvement. Experimental results show that Bi and carbon vacancy carbon nitride play a role in photocatalysis synergistically. Bi as a plasma metal can concentrate incident photon energy into plasma oscillation, and the concentrated resonance energy can be transferred to V-CN or converted into a local electromagnetic field, which is also beneficial to e ‑ /h + Separation in V-CN.
Description
Technical Field
The invention belongs to the technical field of inorganic functional material preparation, and particularly relates to a preparation method and application of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye.
Background
Future development of human society will face problems of energy shortage and environmental pollution, however, photocatalytic technology is considered as the most promising technology for solving this threat. Through research and study in recent decades, the photocatalytic technology has wide application prospects in the fields of hydrogen production by utilizing sunlight to decompose water, reduction of carbon dioxide into a large amount of recyclable mono-carbon compounds and di-carbon compounds, organic synthesis under mild conditions and the like. The use of a suitable photocatalyst is important for the photocatalytic process. Bulk bismuth (Bi) is a typical semimetal with specific electronic and optical properties. In recent years, Bi has received much attention due to its unique properties such as anisotropy, long mean free path, small electron effective mass, low carrier density, and very small band overlap energy. Therefore, Bi is widely used to study quantum confinement effects. The transition from semi-metal to semiconductor is made by the reduction of crystallite size below a critical value. Further, like Ag and Au, Bi has also been confirmed to have plasma properties. Surface Plasmon Resonance (SPR) effects can be generated by the collective excitation of free electrons in Bi, resulting in strong resonant optical absorption. To date, many studies report that metal Bi performs two functions in photocatalytic systems: one as a co-catalyst and the other as a direct plasma photocatalyst.
As a direct plasma photocatalyst, Bi has received extensive attention and extensive research. However, double nanoparticles tend to agglomerate due to thermodynamic instability, which impairs their function and limits their application. Therefore, loading nanoparticles onto a support having a high specific surface is considered to be an effective method for securing high dispersibility and stability of the nanoparticles. It is well known that there are certain limitations on the photocatalytic performance of single phase materials, and therefore it is very attractive to construct hybrid materials by combining metal Bi with other semiconductor materials. The photocatalysis effect is promoted by the combined synergistic effect of the two materials. For example, bismuth may be combined with titanium dioxide, bismuth-based oxides, or other semiconductor photocatalysts, respectively.
In recent years, semiconductor photocatalysts are widely concerned about removing rhodamine B in wastewater due to the advantages of environmental friendliness, high degradation efficiency, thorough degradation, less secondary pollution, short period and the like. Graphitized Carbon Nitride (CN) is a new semiconductor polymer material, and can be excited under visible light due to the small band gap width of only 2.7eV, so that the graphitized Carbon Nitride (CN) is a light-driven catalyst with great development prospect. However, original CN prepared by nitrogen-rich precursor thermal polymerization has a large band gap and a poor specific surface area, and therefore, the photocatalytic performance is not ideal in practical application. Therefore, there is an urgent need to solve these problems and develop a CN-based semiconductor photocatalyst having high photocatalytic efficiency.
The present invention therefore first improves the photocatalytic redox capacity by creating suitable vacancy sites in the CN polymer framework. Secondly, the characteristics of small electron effective mass, low carrier concentration, long mean free path, anisotropy, plasma (SPR) effect and the like of bismuth metal are utilized to load the nano bismuth on the carbon defect carbon nitride polymer, and the preparation of the metal Bi loaded carbon defect carbon nitride catalyst and the structural characteristics, the morphological characteristics, the optical characteristics and the electrochemical characteristics of the metal Bi loaded carbon defect carbon nitride catalyst are found.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye, which has simple and convenient preparation process and is easy to adjust.
The invention also aims to provide application of the bismuth-loaded carbon-defect carbon nitride capable of degrading dye in a photocatalytic manner.
The scheme adopted by the invention for realizing one of the purposes is as follows: a preparation method of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye comprises the steps of firstly obtaining carbon-defect carbon nitride with a loose structure through a high-temperature thermal polymerization method, and then loading bismuth simple substance on the carbon-defect carbon nitride through a chemical reduction method.
Preferably, the method comprises the following steps:
(1) calcining the carbon nitride precursor at a certain temperature, and grinding the calcined carbon nitride precursor to obtain fine carbon defect carbon nitride powder;
(2) placing the carbon-defect carbon nitride powder obtained in the step (1) and a bismuth source in a solvent, and stirring at a certain temperature to uniformly disperse the bismuth source in the carbon-defect carbon nitride solution;
(3) and after the solution is cooled, dripping a sodium borohydride solution or a hydrazine hydrate solution into the solution, continuing to react until the reaction is complete, and filtering, washing and drying a product to obtain the bismuth-loaded carbon-defect carbon nitride.
The carbon nitride with loose structure and carbon defect on the surface is obtained by calcining the precursor at high temperature. Calcination was carried out in a capped 100ml quartz crucible with defective carbon nitride. Then loading the simple substance bismuth on carbon-defect carbon nitride by a chemical reduction method
Preferably, in the step (1), the precursor is any one of melamine, dicyandiamide and urea.
Preferably, in the step (1), the calcination temperature is 600-620 ℃, and the heat preservation time is 4-6 hours.
Preferably, in the step (2), the bismuth source used is bismuth nitrate pentahydrate.
Preferably, in the step (2), the mass percentage of the bismuth source in the carbon-defect carbon nitride is 0.5% -2.0%.
Preferably, in the step (2), the solvent is a mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1-2: 1.
Preferably, in the step (2), the bismuth source is stirred at room temperature, then the temperature is raised to 80-100 ℃, and the stirring is continued until the bismuth source is fully dissolved.
Preferably, in the step (3), the concentration of the sodium borohydride solution or the hydrazine hydrate solution is 0.1-0.5g/ml, and the molar ratio of the sodium borohydride or the hydrazine hydrate to the bismuth source is 83:1-27: 1.
The second scheme adopted by the invention for realizing the purpose is as follows: the application of the bismuth-loaded carbon-defect carbon nitride prepared by the preparation method is used for photocatalytic degradation of rhodamine B.
The invention has the following advantages and beneficial effects:
according to the preparation method, carbon nitride with carbon defects on the surface is obtained by a high-temperature thermal polymerization method, a defect engineering strategy is utilized to introduce carbon vacancies into graphite-phase Carbon Nitride (CN), and then a chemical reduction method is adopted to prepare elemental Bi-loaded carbon-defect carbon nitride (Bi-V-CN). Elemental Bi-loaded carbon-deficient carbon nitride has the following advantages: the introduction of defects will further destroy some in-plane triazine structures, form holes, and increase photo-generated electrons. g-C 3 N 4 The ultra-thin structure of (2) can rapidly transfer carriers from the inside of the semiconductor to the surface of the semiconductor. Due to the heterogeneous coordination with high atomic activity, surface defects are generally used as active sites for activating reactant molecules and can inhibit the surface recombination of carriers, resulting in a greatly reduced recombination rate. Bi as a plasma metal can concentrate incident photon energy into plasma oscillation, and the concentrated resonance energy can be transferred to V-CN or converted into a local electromagnetic field, which is also beneficial to the separation of e-/h + in V-CN.
The preparation method of the invention introduces surface defects and metal loading, and the prepared bismuth-loaded carbon-deficient carbon nitride has an active phase g-C for photocatalytic degradation of rhodamine B 3 N 4 There is a great improvement. Experimental results show that Bi and carbon vacancy carbon nitride play a role in synergy in photocatalysis. Bi as a plasma metal can concentrate incident photon energy into plasma oscillation, and the concentrated resonance energy can be transferred to V-CN or converted into a local electromagnetic field, which is also beneficial to e - /h + Separation in V-CN.
The preparation method does not need to carry out a mixed grinding process on the raw materials, has simple production process and short production period, and is beneficial to reducing the production cost.
Drawings
FIG. 1 is an elemental analysis chart of bulk-phase Carbon Nitride (CN) and carbon-deficient carbon nitride (V-CN) obtained in example 1 of the present invention;
FIG. 2 XRD patterns of bulk phase Carbon Nitride (CN), carbon deficient carbon nitride (V-CN) and bismuth-supported carbon deficient carbon nitride (Bi-V-CN) obtained from example 1 of the present invention;
FIG. 3 is an infrared spectrum of bulk Carbon Nitride (CN), carbon deficient carbon nitride (V-CN) and bismuth-supported carbon deficient carbon nitride (Bi-V-CN) obtained in example 1 of the present invention;
FIG. 4 shows paramagnetic electron resonance spectra of bulk Carbon Nitride (CN), carbon-deficient carbon nitride (V-CN) and bismuth-supported carbon-deficient carbon nitride (Bi-V-CN) obtained in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph and a transmission electron micrograph of bulk-phase Carbon Nitride (CN), carbon-deficient carbon nitride (V-CN) and bismuth-supported carbon-deficient carbon nitride (Bi-V-CN) obtained in example 1, wherein the scanning electron micrographs are for pure CN, V-CN and Bi-V-CN, respectively, as shown in FIGS. (a), (b) and (c), and the TEM images for pure CN, V-CN and Bi-V-CN, respectively, as shown in FIGS. (d), (e) and (f);
FIG. 6 is a graph showing the results of elemental analysis using SEM-EDS and elemental mapping for bismuth-supported carbon-deficient carbon nitride (Bi-V-CN);
FIG. 7 is an electrochemical photo-amperometric graph of bulk-phase Carbon Nitride (CN), carbodeficient carbon nitride (V-CN) and bismuth-supported carbodeficient carbon nitride (Bi-V-CN) obtained in example 1;
FIG. 8 is a graph showing the electrochemical impedance of bulk Carbon Nitride (CN), carbon-deficient carbon nitride (V-CN), and bismuth-supported carbon-deficient carbon nitride (Bi-V-CN) obtained in example 1.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
(1) Placing 15g of melamine into a 100ml quartz crucible with a cover, and placing the quartz crucible into a muffle furnace for calcination, wherein the calcination temperature is 600 ℃, the heat preservation time is 4 hours, and the heating rate is 2 ℃/min;
(2) grinding for 30min to obtain fine carbon-defect carbon nitride powder;
(3) placing carbon nitride and bismuth nitrate pentahydrate into a mixed solution of ethylene glycol and water, wherein the ratio of ethylene glycol to water is 1:1, and stirring for 30min at room temperature; then heating to 80 ℃, and stirring for 60 min; the mass percentage of the bismuth nitrate pentahydrate in the carbon defect carbon nitride is 0.5 percent,
(4) after cooling, 50ml of sodium borohydride solution with the concentration of 0.1g/ml is taken and slowly dripped into the solution, and the reaction is continued for 4 hours at the dripping speed of 0.5 ml/min.
FIG. 1 is an elemental analysis chart of bulk-phase carbon nitride and carbon-deficient carbon nitride obtained in example 1 of the present invention, in which the C/N ratio is decreased from 0.66 to 0.64, indicating that the carbon content in V-CN is decreased. This is mainly because at high temperature of 600 ℃ and with a slow temperature rise rate, carbon C exposed to air is easily combined with oxygen and is separated from the skeleton to form amorphous carbon or carbon dioxide CO 2 。
Figure 2 XRD patterns of bulk phase carbon nitride, carbon deficient carbon nitride and bismuth supported carbon deficient carbon nitride obtained from example 1 of the present invention. The XRD patterns of all samples showed two typical diffraction peaks, located at about 13.1 ° and 27.5 °, respectively, corresponding to the in-plane structural stacking motif (100) and the interlayer stacking motif (002) of the conjugated aromatic system, respectively. At the same time, all modified samples had unique diffraction peaks similar to CN, indicating that doping of bismuth and introduction of carbon vacancies hardly destroyed the basic backbone of CN. However, the diffraction intensity of the modified sample was generally reduced. The change from CN to CN-V is due to the lamellar structure. The resulting change is not particularly significant due to the incorporation of Bi into the plane of V-CN, which may be due to a relatively low doping level of Bi.
FIG. 3 is an infrared spectrum of bulk carbon nitride, carbon-deficient carbon nitride and bismuth-supported carbon-deficient carbon nitride obtained in example 1 of the present invention. 811cm -1 Is a characteristic telescopic shock absorption peak belonging to an s-triazine structure; 1240-1570 cm -1 Belongs to the telescopic vibration of C-N heterocyclic ring frameworks; 888cm -1 And 1635cm -1 The vibration modes of (A) correspond to the stretching vibration of N-H and C-N respectively; 3000-3400 cm -1 Is a tensile vibration belonging to N-H; in addition, 1240-1650 cm -1 Is influenced by the simple substance of BiHowever, since the doping amount is low, the variation is not significant. And the characteristic peaks of the three materials are basically consistent, which again shows that the basic characteristic structure of the carbon nitride is not influenced by the co-introduction of Bi and carbon vacancy.
FIG. 4 shows the paramagnetic electron resonance spectra of bulk carbon nitride, carbon-deficient carbon nitride and bismuth-supported carbon-deficient carbon nitride obtained in example 1 of the present invention. The EPR signal increases when g is 2.002, with the gradual increase in the EPR signal from CN to V-CN to Bi-V-CN indicating a relative increase in the concentration of lone-pair electrons induced by unpaired electrons on the carbon atom aromatic rings in the nanocluster and the plasma effect of Bi.
FIG. 5 is a scanning electron micrograph and a transmission electron micrograph of bulk-phase carbon nitride, carbo-deficient carbon nitride and bismuth-supported carbo-deficient carbon nitride obtained in example 1, as shown in (a), (b) and (c) are scanning electron micrographs of bulk-phase carbon nitride, carbo-deficient carbon nitride and bismuth-supported carbo-deficient carbon nitride, respectively, and as shown in the figure, pure CN, V-CN and Bi-V-CN samples all have a layered structure. The samples of V-CN and Bi-V-CN have a much thinner layer than CN, and contain some porous structures which can provide more active sites for the photocatalytic reaction. To further demonstrate that the current synthesis conditions are conducive to the introduction of carbon defects and bismuth metal, it can be deduced from the graph (c) that the synthesized Bi-V-CN consists of a large number of solid particles having a diameter of 200 to 250 nm. TEM images of CN, V-CN and Bi-V-CN are provided in FIGS. (d), (e) and (f), respectively. It can be seen that V-CN is composed of flakes, and therefore this will favor the growth of Bi metal particles on its surface.
FIG. 6 is an elemental analysis of Bi-V-CN using SEM-EDS and elemental mapping. It can be seen that the Bi metal with the diameter of 150-200 nm is uniformly dispersed on the V-CN, further indicating that the Bi element exists in a simple substance state.
Fig. 7 is an electrochemical photo-amperometric graph of bulk-phase carbon nitride, carbon-deficient carbon nitride and bismuth-supported carbon-deficient carbon nitride obtained in example 1. When the light source is turned on or off, the photocurrent from CN, V-CN to Bi-V-CN is continuously increased due to the effective separation of the current carriers, which shows that the photocatalytic performance is also gradually improved. In addition, the photocurrent of the sample does not significantly decay under cycling, with good repeatability.
Fig. 8 is an electrochemical impedance plot of bulk-phase carbon nitride, carbon-deficient carbon nitride, and bismuth-supported carbon-deficient carbon nitride obtained in example 1. The arc radius on the EIS Nyquist plot for Bi-V-CN is significantly smaller than for CN and V-CN, reflecting the relatively small charge transfer resistance of Bi-V-CN from the electrode to the electrolyte molecules. This is because Bi-V-CN has enhanced conductivity, and these conclusions indicate that having carbon vacancies and bismuth Bi synergistically provides Bi-V-CN with efficient electron vacancy, hole pair separation and fast charge transfer at the interface.
Example 2
(1) Placing 15g of urea into a 100ml quartz crucible with a cover, and calcining in a muffle furnace at 600 ℃ for 4 hours at a heating rate of 3 ℃/min;
(2) grinding for 30min to obtain fine carbon-defect carbon nitride powder;
(3) placing carbon nitride and bismuth nitrate pentahydrate into a mixed solution of ethylene glycol and water, wherein the ratio of the ethylene glycol to the water is 1.5:1, and stirring for 30min at room temperature; then heating to 100 ℃, and stirring for 60 min; the mass percentage of the bismuth nitrate pentahydrate in the carbon defect carbon nitride is 1.0 percent;
(4) after cooling, 50ml of hydrazine hydrate solution with the concentration of 0.1g/ml is slowly dripped into the solution, and the reaction is continued for 4 hours at the dripping speed of 0.5 ml/min.
Example 3
(1) Placing 15g of dicyandiamide in a 100ml quartz crucible with a cover, and placing the quartz crucible in a muffle furnace for calcination, wherein the calcination temperature is 620 ℃, the heat preservation time is 6 hours, and the heating rate is 4 ℃/min;
(2) grinding for 30min to obtain fine carbon-defect carbon nitride powder;
(3) placing carbon nitride and bismuth nitrate pentahydrate into a mixed solution of ethylene glycol and water, wherein the ratio of ethylene glycol to water is 2:1, and stirring for 30min at room temperature; then heating to 90 ℃, stirring for 60min, wherein the mass percent of the pentahydrate bismuth nitrate in the carbon defect carbon nitride is 2.0%;
(4) after cooling, 50ml of sodium borohydride solution with the concentration of 0.2g/ml is taken and slowly dripped into the solution, and the reaction is continued for 4 hours at the dripping speed of 0.5 ml/min.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A preparation method of bismuth-loaded carbon-defect carbon nitride capable of photocatalytic degradation of dye is characterized by comprising the following steps: firstly, carbon-deficient carbon nitride with a loose structure is obtained through a high-temperature thermal polymerization method, and then bismuth is loaded on the carbon-deficient carbon nitride through a chemical reduction method.
2. The method of preparing a bismuth-supported carbon-deficient carbon nitride of a photocatalytically degradable dye according to claim 1, comprising the steps of:
(1) calcining the carbon nitride precursor at a certain temperature, and grinding the calcined carbon nitride precursor to obtain fine carbon defect carbon nitride powder;
(2) placing the carbon-defect carbon nitride powder obtained in the step (1) and a bismuth source in a solvent, and stirring at a certain temperature to uniformly disperse the bismuth source in the carbon-defect carbon nitride solution;
(3) and after the solution is cooled, dripping a sodium borohydride solution or a hydrazine hydrate solution into the solution, continuing to react until the reaction is complete, and filtering, washing and drying a product to obtain the bismuth-loaded carbon-defect carbon nitride.
3. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (1), the precursor is any one of melamine, dicyandiamide and urea.
4. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (1), the calcination temperature is 600-620 ℃, and the heat preservation time is 4-6 hours.
5. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (2), the bismuth source is bismuth nitrate pentahydrate.
6. The method for preparing bismuth-supported carbon-defect carbon nitride of a photocatalytically degradable dye according to claim 2, characterized in that: in the step (2), the bismuth source accounts for 0.5-2.0% of the carbon-defect carbon nitride by mass.
7. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (2), the solvent is a mixed solution of ethylene glycol and water, wherein the volume ratio of the ethylene glycol to the water is 1-2: 1.
8. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (2), stirring is carried out at room temperature, then the temperature is raised to 80-100 ℃, and stirring is continued until the bismuth source is fully dissolved.
9. The method of preparing a bismuth-supported carbon-deficient carbon nitride that is a photocatalytically degradable dye according to claim 2, wherein: in the step (3), the concentration of the sodium borohydride solution or the hydrazine hydrate solution is 0.1-0.5g/ml, and the molar ratio of the sodium borohydride or the hydrazine hydrate to the bismuth source is 83:1-27: 1.
10. Use of a bismuth-supported carbon-deficient carbon nitride prepared by the preparation method according to any one of claims 1 to 9, wherein: the method is used for photocatalytic degradation of rhodamine B.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104607240A (en) * | 2015-02-12 | 2015-05-13 | 重庆工商大学 | Bi/g-C3N4 semimetal-organic composite photocatalyst and preparation method |
| CN108704656A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification and its application during producing hydrogen peroxide |
| CN111044586A (en) * | 2019-11-06 | 2020-04-21 | 江苏大学 | Preparation method of bismuth-doped polymeric carbon nitride nanocomposite material containing carbon defects |
| CN111203260A (en) * | 2020-02-25 | 2020-05-29 | 广州中国科学院沈阳自动化研究所分所 | Monoatomic palladium-supported carbon nitride catalyst, preparation thereof and application thereof in removing NO |
| EP3848122A1 (en) * | 2020-01-09 | 2021-07-14 | Nankai University | Visible light catalytic material and preparation method and application thereof |
-
2022
- 2022-06-21 CN CN202210703775.XA patent/CN114904560A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586064A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Metal/graphite-like carbon nitride compound catalyst and preparing method thereof |
| CN104607240A (en) * | 2015-02-12 | 2015-05-13 | 重庆工商大学 | Bi/g-C3N4 semimetal-organic composite photocatalyst and preparation method |
| CN108704656A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of surface carbon vacancy modification and its application during producing hydrogen peroxide |
| CN111044586A (en) * | 2019-11-06 | 2020-04-21 | 江苏大学 | Preparation method of bismuth-doped polymeric carbon nitride nanocomposite material containing carbon defects |
| EP3848122A1 (en) * | 2020-01-09 | 2021-07-14 | Nankai University | Visible light catalytic material and preparation method and application thereof |
| CN111203260A (en) * | 2020-02-25 | 2020-05-29 | 广州中国科学院沈阳自动化研究所分所 | Monoatomic palladium-supported carbon nitride catalyst, preparation thereof and application thereof in removing NO |
Non-Patent Citations (1)
| Title |
|---|
| 李雪艳等: ""碳空位改性C3N4的制备及光催化性能"", 《大连工业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116474809A (en) * | 2023-04-12 | 2023-07-25 | 江苏大学 | Preparation method and application of bismuth nanoparticle modified carbon nitride photocatalyst |
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