CN110841670A - Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof - Google Patents
Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof Download PDFInfo
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- 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
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and a preparation method thereof. The preparation method comprises the following steps: and mixing the one-dimensional tubular carbon nitride with the zero-dimensional black phosphorus quantum dot solution, and drying in vacuum to obtain the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst. The composite photocatalyst has the advantages of strong light absorption capacity, strong photo-generated carrier separation and migration capacity, high photocatalytic activity, good stability and the like, can be widely used for catalytic reduction of heavy metal pollutants and degradation of organic pollutants, can effectively remove the heavy metal pollutants and the organic pollutants from a medium, and has high use value and application prospect. The preparation method has the advantages of simple process, convenient operation, low cost, no secondary pollution to the environment and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of visible light catalysis, and relates to a zero-dimensional black phosphorus quantum dot one-dimensional tubular carbon nitride composite photocatalyst and a preparation method thereof.
Background
Compared with non-renewable fuels such as petroleum and coal, solar energy is a continuous clean energy source and is an important object of green clean energy research. In the past decades, photocatalytic technology with high economic benefit and environmental friendliness has become a hot point of research and has been well applied to wastewater treatment. The photocatalysis technology is a technology capable of converting solar energy into chemical energy, namely, an advanced oxidation technology for catalyzing chemical reaction to efficiently carry out by using a photocatalyst which can participate in the chemical reaction but can keep the photocatalyst unchanged under the illumination condition. The photocatalytic reaction has the potential for large-scale application because the technology can efficiently catalyze the reaction and consumes energy mainly from solar energy in the catalytic reaction process.
The carbon nitride material is a non-metal polymer composed of nitrogen element (N) and carbon element (C), and belongs to semiconductor materials. Wherein the graphite phase g-C3N4Has special structure and energy band position, has the advantages of convenient modification, acid and alkali resistance, good economic benefit and the like, and is g-C3N4Superior to traditional metal catalysts, also in g-C3N4The material is one of the reasons for the main photocatalyst. However, monomers g to C3N4Has a number of disadvantages including large particle size, small specific surface area and rapid recombination of photogenerated electron-hole pairs, which reduces g-C in photocatalysis3N4The electron utilization efficiency of (2). To increase the monomer g-C3N4The method for modifying the photocatalytic activity comprises the methods of morphology regulation, element doping, semiconductor coupling, protonation and the like, and the one-dimensional tubular carbon nitride is constructed through the morphology regulation, so that the problems can be effectively overcome, more active sites can be provided, and the photocatalytic reaction can be better carried out.
Black Phosphorus (BP), a two-dimensional layered material having excellent electrical and optical properties, has a graphene-based layered structure, and has a forbidden band width that varies with the shape of BP. For the monomer BP, the forbidden band width is 0.34 eV; for a single layer of BP, the forbidden band width is 1.5 eV. Thus, BP photocatalysts have a g-C ratio higher than normal3N4And the spectral absorption edge can be in a far infrared band in a wider spectral response range. Because of exhibiting attractive optical and optoelectronic propertiesThe desirability of high mechanical strength is favorable for the repeated use of BP in practice, so that the potential of BP in photocatalytic applications is not a little great deal. Besides the advantages of layered BP, the BP quantum dot also has the advantages of quantum confinement effect, edge protrusion, high absorption coefficient and the like. In addition, the composite material formed by the existing zero-dimensional black phosphorus quantum dots and carbon nitride still has the problems of insufficient photocatalytic activity, poor stability and the like, which greatly limits the wide application of the photocatalytic technology. Therefore, the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst which has strong light absorption capacity, strong photocarrier separation and migration capacity, high photocatalytic activity and good stability has important significance for improving the effect of the photocatalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst with strong light absorption capacity, strong photogenerated carrier separation and migration capacity, high photocatalytic activity and good stability and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst comprises one-dimensional tubular carbon nitride; zero-dimensional black phosphorus quantum dots are modified on the one-dimensional tubular carbon nitride.
As a general technical concept, the invention also provides a preparation method of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst, which comprises the following steps: and mixing the one-dimensional tubular carbon nitride with the zero-dimensional black phosphorus quantum dot solution, and drying in vacuum to obtain the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst.
The preparation method is further improved, and the mass-volume ratio of the one-dimensional tubular carbon nitride to the zero-dimensional black phosphorus quantum dot solution is 0.15 g: 8-12 mL; the concentration of the zero-dimensional black phosphorus quantum dot solution is 0.1 mg/mL-0.2 mg/mL.
In the above preparation method, further improvement is that the preparation method of the one-dimensional tubular carbon nitride comprises the following steps:
s1, dissolving urea and melamine in water, and performing ultrasonic treatment and stirring to obtain a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, and drying to obtain a precursor;
and S3, calcining the precursor obtained in the step S2 to obtain the one-dimensional tubular carbon nitride.
In the above preparation method, further improvement is provided, in the step S1, the mass ratio of urea to melamine is 3: 1; the ultrasonic time is 2.5-3.5 h; the stirring speed is 300 r/min-500 r/min; the stirring time is 10-12 h.
In a further improvement of the above preparation method, in step S2, the hydrothermal reaction is performed at a temperature of 180 ℃; the hydrothermal time is 18-20 h; the drying is carried out at the temperature of 60-70 ℃; the drying time is 8-10 h.
In the above preparation method, further improvement, in the step S3, the temperature rise rate in the calcination process is 2 ℃/min to 5 ℃/min; the calcining temperature is 500-600 ℃; the calcining time is 4-6 h.
In the preparation method, the preparation method of the zero-dimensional black phosphorus quantum dot solution is further improved, and comprises the following steps:
(1) grinding the black phosphorus crystal, adding water, and performing ultrasonic treatment to obtain a black phosphorus crystal suspension;
(2) and (3) centrifuging the black phosphorus crystal suspension obtained in the step (1), and removing black phosphorus nanosheets to obtain a zero-dimensional black phosphorus quantum dot solution.
In the above preparation method, further improvement is provided, in the step (1), the grinding time is 0.5h to 1 h; the ultrasonic time is 15-18 h;
in the step (2), the rotation speed of the centrifugal treatment is 5000 r/min-5500 r/min; the time of the centrifugal treatment is 6-8 min.
In the preparation method, the mixing is carried out under ice bath conditions; the temperature of the system is controlled to be 10-20 ℃ in the mixing process; the mixing time is 6-8 h; the temperature of the vacuum drying is 40-45 ℃; the vacuum drying time is 8-12 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst which comprises one-dimensional tubular carbon nitride, wherein the zero-dimensional black phosphorus quantum dot is modified on the one-dimensional tubular carbon nitride. In the invention, the one-dimensional tubular carbon nitride has larger specific surface area and more active sites, which is beneficial to photocatalytic reaction, and meanwhile, the zero-dimensional black phosphorus quantum dot has the advantages of good optical property, electrical property, quantum confinement effect and the like, and the zero-dimensional black phosphorus quantum dot is loaded on the one-dimensional tubular carbon nitride and is used as an electron medium, so that photo-generated electrons and holes generated by the one-dimensional tubular carbon nitride under illumination can be separated more quickly, and better photocatalytic activity is obtained. The zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst has the advantages of strong light absorption capacity, strong photogenerated carrier separation and migration capacity, high photocatalytic activity, good stability and the like, can be widely used for catalytic reduction of heavy metal pollutants and degradation of organic pollutants, can effectively remove the heavy metal pollutants and the organic pollutants from a medium, and has high use value and application prospect.
(2) The zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst can be used for photocatalytic degradation of organic pollutants in the environment and photocatalytic reduction of heavy metals in the environment, can obtain a good treatment effect, and has a high use value and a good application prospect. By taking the heavy metal hexavalent chromium ions as an example, the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst is adopted for reduction for 60min, the reduction rate of the heavy metal hexavalent chromium ions is up to 94.71%, the high-efficiency reduction of the heavy metal hexavalent chromium ions is realized, and the practical application requirements can be met.
(3) The invention also provides a preparation method of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst, which takes the one-dimensional tubular carbon nitride and the zero-dimensional black phosphorus quantum dot solution as raw materials, and the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst with strong light absorption capacity, strong photocarrier separation and migration capacity, high photocatalytic activity and good stability can be prepared by ice bath mixing and vacuum drying. The zero-dimensional black phosphorus quantum dots prepared by the preparation method disclosed by the invention are uniform in size and can be uniformly dispersed on the one-dimensional tubular carbon nitride, so that the zero-dimensional black phosphorus quantum dots/one-dimensional tubular carbon nitride composite photocatalysis has the advantages of large specific surface area, large number of holes, many active sites and the like, and shows very good stability. The preparation method has the advantages of simple process, convenient operation, low cost, no secondary pollution to the environment and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a TEM image of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (d) prepared in example 1 of the present invention, the zero-dimensional black phosphorus quantum dot solution (a), the layered carbon nitride (b) prepared in comparative example 1, and the one-dimensional tubular carbon nitride (c) prepared in comparative example 2.
FIG. 2 is XRD diagrams of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3.
FIG. 3 is a UV-visible diffuse reflection diagram of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3.
FIG. 4 is an electrical impedance diagram of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3.
FIG. 5 is a diagram showing the photocatalytic reduction effect of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3 on a hexavalent chromium ion solution.
Fig. 6 is an XRD comparison graph of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10) prepared in this example 1 before and after treatment of a heavy metal hexavalent chromium ion solution.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, unless otherwise specified, the raw materials and equipment used were commercially available, the process used was a conventional one, the equipment used was conventional, and the data obtained were average values of three or more repeated experiments.
Example 1
A zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst comprises one-dimensional tubular carbon nitride, wherein the zero-dimensional black phosphorus quantum dot is modified on the one-dimensional tubular carbon nitride.
The preparation method of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10) of the embodiment comprises the following steps:
(1) preparing one-dimensional tubular carbon nitride:
(1.1) taking 3g of urea and 1g of melamine, grinding, dissolving in 50mL of deionized water, performing ultrasonic treatment for 2.5h, and uniformly stirring at a rotating speed of 300r/min for 10h to prepare a uniform mixed solution.
(1.2) transferring the mixed solution obtained in the step (1.1) to a 100mL autoclave, preserving the temperature for 20 hours at 180 ℃, naturally cooling, washing with water and ethanol for 3 times respectively, filtering, and drying at 60 ℃ for 8 hours to obtain a precursor.
And (1.3) placing the precursor obtained in the step (1.2) into a crucible and placing the crucible into a muffle furnace according to the heating rate of 2.3 ℃/min, heating to 550 ℃, calcining for 4h, cooling, and grinding to obtain the one-dimensional tubular carbon nitride.
(2) Preparing a zero-dimensional black phosphorus quantum dot solution:
(2.1) grinding the black phosphorus crystal for 0.5h, adding water, and performing ultrasonic treatment for 15h to obtain a black phosphorus crystal suspension;
and (2.2) carrying out centrifugal treatment on the black phosphorus crystal suspension obtained in the step (2.1) for 6min at the rotating speed of 5000r/min, removing black phosphorus nanosheets, and obtaining a zero-dimensional black phosphorus quantum dot solution, which is recorded as BPQDs. The grain diameter of the zero-dimensional black phosphorus quantum dots in the zero-dimensional black phosphorus quantum dot solution is 1 nm-10 nm.
(3) Preparing a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst:
and (2) suspending 0.15g of the one-dimensional tubular carbon nitride prepared in the step (1) in 20mL of ultrapure water, adding 10mL of the zero-dimensional black phosphorus quantum dot solution prepared in the step (2), mixing for 6h under an ice bath condition (10-20 ℃), and vacuum-drying for 12h at the temperature of 40 ℃ to obtain the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst, which is recorded as BPTCN-10.
Example 2:
a preparation method of a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst is basically the same as that in example 1, and the difference is only that: the volume of the zero-dimensional black phosphorus quantum dot solution used in the preparation method of example 2 was 8 mL.
The zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst prepared in the embodiment 2 is marked as BPTCN-8.
Example 3:
a preparation method of a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst is basically the same as that in example 1, and the difference is only that: the volume of the zero-dimensional black phosphorus quantum dot solution used in the preparation method of example 3 was 12 mL.
The zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst prepared in the example 3 is marked as BPTCN-12.
Comparative example 1:
a preparation method of layered carbon nitride comprises the following steps:
putting 2g of melamine into a crucible, placing the crucible in a muffle furnace, heating the crucible to 500 ℃ at the heating rate of 2.3 ℃/min, preserving the heat at 500 ℃ for 4h, taking out the melamine after natural cooling, and grinding the melamine by using a mortar to obtain light yellow layered carbon nitride, which is marked as CN.
Comparative example 2:
a preparation method of a one-dimensional tubular carbon nitride photocatalyst comprises the following steps:
(1) 3g of urea and 1g of melamine are taken, ground and dissolved in 50mL of deionized water, ultrasonic treatment is carried out for 2.5h, and uniform stirring is carried out for 10h at a rotating speed of 300r/min, so as to prepare uniform mixed solution.
(2) And (2) transferring the mixed solution obtained in the step (1) into a 100mL high-pressure kettle, preserving the heat for 20 hours at 180 ℃, naturally cooling, washing with water and ethanol for 3 times respectively, filtering, and drying at 60 ℃ for 8 hours to obtain a precursor.
(3) And (3) putting the precursor obtained in the step (2) into a crucible and placing the crucible into a muffle furnace according to the heating rate of 2.3 ℃/min, heating to 550 ℃, calcining for 4h, cooling, and grinding to obtain one-dimensional tubular carbon nitride, which is recorded as TCN.
Comparative example 3:
a preparation method of a zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst comprises the following steps:
0.15g of the layered carbon nitride prepared in the comparative example 1 is suspended in 20mL of ultrapure water, 10mL of the zero-dimensional black phosphorus quantum dot solution prepared in the example 1 is added, and the mixture is mixed for 6h under an ice bath condition and dried in vacuum at the temperature of 40 ℃ for 12h to obtain the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst, which is marked as BPCN.
And (3) performance testing:
fig. 1 is a TEM image of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (d) prepared in example 1 of the present invention, the zero-dimensional black phosphorus quantum dot solution (a), the layered carbon nitride (b) prepared in comparative example 1, and the one-dimensional tubular carbon nitride (c) prepared in comparative example 2. As can be seen from FIG. 1, FIG. 1(a) represents a TEM image of a zero-dimensional Black Phosphorus Quantum Dot Solution (BPQDs), wherein the circle part in the image is the morphology of the BPQDs and is a black crystal particle with a diameter between 1-10 nm; as shown in fig. 1(b), it can be observed that the layered Carbon Nitride (CN) has stacked layered structures, and the layered structures are thinner and transparent, but no obvious mesoporous structure exists; as can be seen from fig. 1(c), the one-dimensional Tubular Carbon Nitride (TCN) has a good hollow tubular structure, and micropores are distributed on the wall of the tube; FIG. 1(d) is a TEM morphology of a zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10), wherein a black dotted line is the tube wall of the BPTCN-10, the tube wall is thin, and BPQDs with the particle size of 1-10nm can be found in the range of a dotted circle in the graph.
FIG. 2 is XRD diagrams of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3. The XRD pattern can analyze the crystal form and the crystallization degree of a substance by utilizing the X-ray diffraction principle. When X-ray is irradiated on atoms or ions in different substances, a diffraction ring corresponding to the arrangement of atoms in the substances is generated, and an XRD pattern is obtained through signal conversion. FIG. 2 is an XRD pattern of CN, BPCN, TCN, BPTCN-8, BPTCN-10 and BPTCN-12 with 2 θ (in degrees) on the abscissa and intensity on the ordinate. It can be observed from fig. 2 that CN, BPCN, TCN, BPTCN-8, BPTCN-10 and BPTCN-12 all have a strong absorption peak at 2 θ of 27.3 ° (002); at 13.0 ° (100) with 2 θ, there is a weak absorption peak, indicating that several materials have typical g-C3N4Structures in which 2 θ is 27.3 ° corresponding to g-C3N4The crystalline (002) face, which is a reflection of a typical interlayer stack; 2 theta 13.0 deg. corresponds to g-C3N4The crystal (100) plane is a reflection of the in-plane structure filling. The phenomenon of the smaller intensity of the two diffraction peaks for TCN and a series of BPTCN is presumably due to the smaller size of the crystals formed during the polymerization and the thinning of the lamellae. In addition to these two diffraction peaks, a series of BPTCNs had no other significant diffraction peaks, presumably because no other impurities were formed during the preparation and the BPQDs content was low.
FIG. 3 is a UV-visible diffuse reflection diagram of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3. FIG. 3 shows the absorbance of CN, BPCN, TCN, BPTCN-8, BPTCN-10 and BPTCN-12 in the wavelength range of 300-600 nm. The CN and TCN materials have similar light absorption edge band positions, but the TCN has slightly red-shifted edge band positions compared to CN due to the increased amount of visible light absorption caused by the TCN porous structure. Comparing the TCN with a series of BPTCN materials, the response range of the series of BPTCNs to light can reach about 500nm, and the phenomenon of red shift of light absorption side bands is obviously shown on the BPTCNs, because the BPTCNs load the BPQDs with near infrared response, the light response range of the BPTCNs is effectively expanded, visible light can be more fully utilized, but an optimal load proportion exists.
FIG. 4 is an electrical impedance diagram of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3. FIG. 4 shows electrical impedance curves for CN, BPCN, TCN, BPTCN-8, BPTCN-10, and BPTCN-12, where the abscissa and ordinate of the graph represent resistance. The larger the radius of the EIS curve, the higher the impedance, the larger the resistance, and the lower the charge transfer efficiency. The material electrical impedance arc radius is as follows: CN & gtTCN & gtBPCN & gtBPTCN-8 & gtBPTCN-12 & gtBPTCN-10, and a series of BPTCNs all have smaller electrical impedance, which shows that under the synergistic action of BPQDs and TCNs, the separation efficiency and the transfer efficiency of photo-generated charges on the interfaces of a series of BPTCNs are effectively improved. Moreover, the performance of a series of BPTCN materials is superior to that of a zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN).
The photocatalytic reduction efficiency of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3 on the heavy metal hexavalent chromium ion solution was examined.
Weighing the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in the examples 1-3 of the invention, the layered Carbon Nitride (CN) prepared in the comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in the comparative example 2 and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in the comparative example 3, respectively placing 30mg of each of the obtained materials in 30mL of 10mg/L heavy metal hexavalent chromium ion solution (the pH value of the solution is 4.65), placing the reaction system in a visible light source (300W xenon lamp) to carry out photocatalytic reduction reaction for 60min, and finishing the treatment of the heavy metal hexavalent chromium ion solution.
In the process of photocatalytic reduction reaction, 2mL of reaction liquid is taken every 15 minutes, then the reaction solution is subjected to color development reaction, finally, an ultraviolet visible spectrophotometer is used for measuring the absorbance of the color development solution, and the concentration of hexavalent chromium ions is determined, so that the reduction performance of the photocatalytic material is obtained.
FIG. 5 is a diagram showing the photocatalytic reduction effect of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in examples 1-3 of the present invention, the layered Carbon Nitride (CN) prepared in comparative example 1, the one-dimensional Tubular Carbon Nitride (TCN) prepared in comparative example 2, and the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN) prepared in comparative example 3 on a hexavalent chromium ion solution. As shown in FIG. 5, the reaction curves of CN, TCN, BPCN, BPTCN-8, BPTCN-12 and BPTCN-10 as catalysts were sequentially from top to bottom. The CN has the worst reduction capability of photocatalysis Cr (VI), and 22 percent of Cr (VI) can be reduced within 60 min. A series of BPTCN photocatalytic distributions can reduce Cr (VI) from 100% to about 5%, and obviously, the capacity of the series of BPTCN photocatalytic reduction Cr (VI) is better. Meanwhile, as can be seen from fig. 5, the reduction effect of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-8, BPTCN-10, BPTCN-12) prepared in embodiments 1 to 3 of the present invention on heavy metal Cr (vi) is significantly better than that of the zero-dimensional black phosphorus quantum dot/layered carbon nitride composite photocatalyst (BPCN), and the increase range is 5% to 15%, because the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst has a larger specific surface area and more active sites, and thus can adsorb more black phosphorus quantum dots and absorb more photons, thereby improving the light absorption performance and the photocatalytic performance.
X-ray diffraction analysis is carried out on the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10) before and after heavy metal hexavalent chromium ions are treated, and the result is shown in figure 6. Fig. 6 is an XRD comparison graph of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10) prepared in this example 1 before and after treatment of a heavy metal hexavalent chromium ion solution. As shown in FIG. 6, the X-ray diffraction patterns of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst (BPTCN-10) before and after the reaction are kept unchanged, and the peaks are sharp, which shows that the structure before and after the reaction is kept unchanged, the crystallinity is good, and the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst has good stability. In addition, the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst still shows a very good reduction effect after being used for treating a heavy metal hexavalent chromium ion solution for multiple times, which also indicates that the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst has very good stability.
In conclusion, the invention provides the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst which is a novel photocatalytic material with good stability and good photocatalytic performance, has a unique morphology structure, a large specific surface area, an excellent pore structure and better photo-generated carrier separation and migration capabilities, can realize efficient and thorough reduction of heavy metal pollutants under visible light, and has a wide prospect in the field of photocatalysis.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst is characterized by comprising one-dimensional tubular carbon nitride; zero-dimensional black phosphorus quantum dots are modified on the one-dimensional tubular carbon nitride.
2. The preparation method of the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst as claimed in claim 1, which is characterized by comprising the following steps: and mixing the one-dimensional tubular carbon nitride with the zero-dimensional black phosphorus quantum dot solution, and drying in vacuum to obtain the zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst.
3. The preparation method according to claim 2, wherein the mass-to-volume ratio of the one-dimensional tubular carbon nitride to the zero-dimensional black phosphorus quantum dot solution is 0.15 g: 8 mL-12 mL; the concentration of the zero-dimensional black phosphorus quantum dot solution is 0.1 mg/mL-0.2 mg/mL.
4. The method according to claim 3, wherein the method for preparing one-dimensional tubular carbon nitride comprises the steps of:
s1, dissolving urea and melamine in water, and performing ultrasonic treatment and stirring to obtain a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, and drying to obtain a precursor;
and S3, calcining the precursor obtained in the step S2 to obtain the one-dimensional tubular carbon nitride.
5. The method according to claim 4, wherein in step S1, the mass ratio of urea to melamine is 3: 1; the ultrasonic time is 2.5-3.5 h; the stirring speed is 300 r/min-500 r/min; the stirring time is 10-12 h.
6. The method according to claim 5, wherein in the step S2, the hydrothermal reaction is performed at a temperature of 180 ℃; the hydrothermal time is 18-20 h; the drying is carried out at the temperature of 60-70 ℃; the drying time is 8-10 h.
7. The method according to claim 6, wherein in step S3, the temperature increase rate during the calcination is 2 ℃/min to 5 ℃/min; the calcining temperature is 500-600 ℃; the calcining time is 4-6 h.
8. The preparation method of claim 3, wherein the preparation method of the zero-dimensional black phosphorus quantum dot solution comprises the following steps:
(1) grinding the black phosphorus crystal, adding water, and performing ultrasonic treatment to obtain a black phosphorus crystal suspension;
(2) and (3) centrifuging the black phosphorus crystal suspension obtained in the step (1), and removing black phosphorus nanosheets to obtain a zero-dimensional black phosphorus quantum dot solution.
9. The method according to claim 8, wherein in the step (1), the grinding time is 0.5 to 1 hour; the ultrasonic time is 15-18 h;
in the step (2), the rotation speed of the centrifugal treatment is 5000 r/min-5500 r/min; the time of the centrifugal treatment is 6-8 min.
10. The method according to any one of claims 2 to 9, wherein the mixing is performed under ice bath conditions; the temperature of the system is controlled to be 10-20 ℃ in the mixing process; the mixing time is 6-8 h; the temperature of the vacuum drying is 40-45 ℃; the vacuum drying time is 8-12 h.
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