CN108355702B - Graphite-phase carbon nitride photocatalyst with large specific surface area carbon deposition defects and preparation method and application thereof - Google Patents
Graphite-phase carbon nitride photocatalyst with large specific surface area carbon deposition defects and preparation method and application thereof Download PDFInfo
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- 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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Abstract
The invention discloses a graphite-phase carbon nitride photocatalyst with carbon deposition defects on a large specific surface area, and a preparation method and application thereof. The method comprises the following specific steps: dropwise adding nitric acid into the graphite-phase carbon nitride to obtain a mixed solution; and carrying out hydrothermal treatment on the mixed solution at a certain temperature to obtain solid powder, and drying the solid powder in an air atmosphere to obtain a target product. The preparation method is simple, the conditions are mild, the industrial production prospect is good, and the obtained graphite-phase carbon nitride photocatalyst can degrade isopropanol to acetone under the irradiation of visible light with the wavelength of more than 420 nm.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a graphite-phase carbon nitride photocatalyst with carbon deposition defects on a large specific surface area, and a preparation method and application thereof.
Background
In recent years, a great deal of research has been devoted to developing a high-efficiency semiconductor photocatalyst and applying it to photocatalytic decomposition of water, degradation of harmful substances and CO2And the like, to solve the increasingly serious global energy and environmental problems. Graphite phase carbon nitride (g-C)3N4) The photocatalyst is a semiconductor photocatalyst responding to visible light, and has the advantages of high chemical stability, thermal stability, photoelectric property and the like, so that the photocatalyst is widely applied to the fields of hydrogen production by decomposing water, carbon dioxide reduction, organic pollutant degradation and the like. However, due to g-C3N4Has small specific surface area (generally less than 10 m)2/g) and easy recombination of photon-generated carriers, and the like, which causes lower photon efficiency and seriously restricts further application of the compound.
The specific surface area of the material is improved, so that the photocatalytic performance can be obviously improved, the catalyst with large specific surface area can provide more surface active sites, and the diffusion distance of a photon-generated carrier is shortened, so that the efficiency of catalytic reaction is greatly improved. Preparation of photocatalytic material into porous material is one of effective methods for increasing specific surface area, and preparation of porous g-C has been common so far3N4The method of (1) is mainly a hard template method and a soft template method. The hard template method generally adopts a nano-casting technology, takes porous silicon oxide as a template, and prepares porous g-C by copying3N4This method is very effective and can raise the specific surface area to 500m2G, but removal of the template requires a hazardous hydrogen fluoride, which prevents its further use. The soft template method mainly adopts surfactant and block copolymer to produce porous g-C3N4However g-C3N4The CN structure of (A) can be extended at high temperature, and the decomposition temperature of the soft template is relative to g-C3N4The condensation temperature is much lower and premature removal of the soft template causes the formed holes to reclose. Therefore, a non-template method was developed to prepare g-C of porous carbon defects3N4Is necessary.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a graphite-phase carbon nitride photocatalyst with carbon deposition defects on a large specific surface area and application of the graphite-phase carbon nitride photocatalyst in degradation of small molecular organic matters, wherein the graphite-phase carbon nitride photocatalyst prepared by the method has a high specific surface area which reaches 41-52m2The aperture is 2-28nm, the preparation method is simple, the conditions are mild, the required equipment is simple, and the industrial production prospect is good, and the obtained graphite-phase carbon nitride photocatalyst can degrade isopropanol to acetone and carbon dioxide under the irradiation of visible light with the wavelength of more than 420 nm.
The technical scheme adopted by the invention is as follows: a graphite phase carbon nitride photocatalyst with large specific surface area carbon defects is prepared by the following steps:
1) and dropwise adding nitric acid into the graphite-phase carbon nitride to obtain a mixed solution.
Preferably, the preparation method of the graphite phase carbon nitride comprises the following steps: the melamine is placed in a crucible and put into a tube furnace, and is roasted for 4-6h at 550 ℃ under the protection of nitrogen.
Preferably, the amount of nitric acid used is 1.2 to 4.0mL of nitric acid per 0.6g of graphite phase carbon nitride.
Preferably, the nitric acid is dripped into the graphite-phase carbon nitride, and the mixture is heated and stirred for 1 to 3 hours in a water bath at the temperature of 80 ℃ to obtain the mixed solution.
2) And placing the mixed solution in a hydrothermal kettle, and heating to obtain solid powder.
Specifically, the mixed solution is placed in a hydrothermal kettle, and hydrothermal reaction is carried out for 10-12h at the temperature of 120-150 ℃ to obtain solid powder.
3) And drying the solid powder in an air atmosphere to obtain a target product.
Specifically, the solid powder is dried for 10-12h at 80-100 ℃ in the air atmosphere to obtain the target product.
The invention has the following beneficial effects: the invention obtains the graphite phase carbon nitride with large specific surface area by a non-template method. The method specifically comprises the steps of treating graphite-phase carbon nitride by using nitric acid (the nitric acid has strong acidity to strip the graphite-phase carbon nitride with a two-dimensional layered structure), and reacting the strong oxidizing property of the nitric acid with carbon atoms on the surface to obtain the graphite-phase carbon nitride with porous carbon defects. The benefits of this approach can be attributed to two aspects: 1. the bulk graphite phase carbon nitride is stripped into thinner nanosheets and the grain size is reduced by the nitric acid. Small nanoparticles result in a large specific surface area; 2. the strong oxidizing property of nitric acid oxidizes carbon atoms on the surface of the material to produce carbon dioxide, which forms defects that facilitate electron capture. The obtained porous graphite-phase carbon nitride with carbon defects with large specific surface area can improve the photocatalytic performance.
The method of the invention can avoid using dangerous chemicals and form a closed porous structure. g-C obtained3N4Has a large specific surface area (41-52 m)2The pore diameter is 2-28nm, and the porous structures provide more reaction sites, so that the rate of degrading isopropanol to acetone under the irradiation of visible light (420nm) reaches 46.761ppm/min and the pure g-C is obtained3N49.5 times of the total weight of the powder.
Drawings
FIG. 1 is an XRD pattern of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
FIG. 2 shows the nitrogen adsorption and desorption isotherms and the corresponding pore size distributions for CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
FIG. 3 is a chart of the UV-Vis spectra of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
FIG. 4 is a graph of the bandgap locations of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
FIG. 5-1 is an SEM image of CN-0(a), ECNV-1.25(b), ECNV-2.5(c) and ECNV-3.75 (d).
FIG. 5-2 is a TEM image of CN-0(e) and ECNV-2.5 (f).
FIG. 6 is an XPS survey of CN-0 and ECNV-2.5.
FIG. 7 is a graph comparing the fine spectra of XPS N element of CN-0 and ECNV-2.5.
FIG. 8 is a comparison of XPS C element fine spectra for CN-0 and ECNV-2.5.
FIG. 9 is an EPR map of CN-0 and ECNV-2.5.
FIG. 10 is the preparation of pure g-C3N4Comparative graphical representation of the activity of the photocatalysts ECNV-1.25, ECNV-2.5 and ECNV-3.75 to degrade isopropanol under visible light irradiation.
FIG. 11 is the preparation of pure g-C3N4The activity of the photocatalysts ECNV-1.25, ECNV-2.5 and ECNV-3.75 for degrading isopropanol is plotted in a histogram under the irradiation of visible light.
Detailed Description
Pure graphite phase carbon nitride (g-C)3N4) The preparation of (1):
2.25g of melamine were placed in an alumina crucible, which was covered, and the covered alumina crucible was placed in a tube furnace and heated to 550 ℃ under nitrogen for 4 hoursThe heating rate is 5 ℃/min to obtain pure g-C3N4(denoted as CV-0).
The prepared pure g-C3N4Performing nitrogen adsorption and desorption test, wherein the nitrogen adsorption and desorption isotherms and the corresponding pore size distribution are shown in FIG. 2, and the test result shows that pure g-C3N4Has a specific surface area of 5.43m2g-1Substantially no pores are present from the pore size distribution map.
Pure g-C3N4SEM test was conducted, and the results are shown in (a) of FIG. 5-1, in which pure g-C is seen3N4Shown as a layered, massive polymer, which is a typical image of graphite phase carbon nitride. Pure g-C3N4Shown in (e) of FIG. 5-2, the results show pure g-C3N4Is a typical non-porous platelet-like structure.
Pure g-C3N4UV-vis tests were carried out and the results are shown in FIG. 3, from which pure g-C is seen3N4While fig. 4 shows a band gap position of 2.76.
Example 1 a graphite phase carbon nitride photocatalyst with large specific surface area carbon defects (nitric acid ═ 1.25ml)
The preparation method comprises the following steps:
1) adding 2.25g of melamine into an alumina crucible, placing the alumina crucible into a tube furnace, roasting the alumina crucible for 4 hours at 550 ℃ in a nitrogen atmosphere, and grinding the mixture to obtain uniform powder g-C3N4。
2) 1.25ml of nitric acid solution was added to 0.6g g-C3N4Heating and stirring for 3h in a water bath at the temperature of 80 ℃ to obtain a mixed solution.
3) Adding the mixed solution into a hydrothermal kettle, putting the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 10-12h at the temperature of 120-150 ℃ to obtain solid powder.
4) Putting the solid powder into an open evaporating dish, putting the evaporating dish into an oven, drying the evaporating dish for 10 to 12 hours at the temperature of between 80 and 100 ℃ in the air atmosphere to obtain a target product, namely the graphite phase carbon nitride photocatalyst g-C with carbon deposition defects on large specific surface area3N4(as ECNV-1.25).
(II) the result of the detection
XRD testing of the product ECNV-1.25 showed that the results are shown in FIG. 1. from FIG. 1, it can be seen that the sample prepared had two diffraction peaks (13 ℃ and 27 ℃ C.), which are typical of graphite phase carbon nitride, with the resulting pure g-C3N4Similarly.
The product ECNV-1.25 was subjected to nitrogen adsorption desorption test, and the results are shown in FIG. 2, which shows a hysteresis loop indicating that ECNV-1.25 has a porous structure and a pore size distribution of 2-28nm, and the test results show that the obtained porous ECNV-1.25 has a size of 41m2Specific surface area in g.
The product ECNV-1.25 was tested by UV-vis, the results are shown in FIG. 3, which shows the comparison with pure g-C3N4The absorption edge of (a) is blue-shifted while figure 4 shows a band gap position of 2.91, illustrating that the band gap is broadened, the lifetime of the photogenerated carriers is extended, and the photocatalytic activity is increased.
The ECNV-1.25 was subjected to SEM test results as shown in (b) of FIG. 5-1, from which it was seen that ECNV-1.25 shows a layered, small block of polymer, which is an image of a typical exfoliated graphite-phase carbon nitride.
(III) application
The prepared ECNV-1.25 photocatalyst is subjected to an isopropanol photocatalytic degradation experiment.
The test process is as follows: using 300W xenon lamp as light source, respectively mixing the prepared photocatalyst (ECNV-1.25) 0.1g and pure g-C3N4Placing in a 4cm container2In the glass tank, the glass tank loaded with the photocatalyst is placed into a 300ml reactor containing atmospheric pressure air, and finally 5ul of isopropanol liquid is injected into the reactor, and the reactor is kept stand for 3 hours to balance the adsorption and desorption of the system, and then the isopropanol is degraded under the irradiation of visible light.
As shown in FIGS. 10 and 11, the lengths of the rectangles in the graph indicate the rate of acetone generation under visible light irradiation, and it can be seen that the graphite-phase carbon nitride having carbon defects with a large specific surface area prepared in example 1 exhibits excellent photocatalytic activity up to 21.821ppm/min, while pure g prepared by the conventional method-C3N4The graphite phase carbon nitride only reaches 4.923 ppm/min.
Example 2 a graphite phase carbon nitride photocatalyst with large specific surface area carbon defects (nitric acid 2.5ml)
The preparation method comprises the following steps:
1) adding 2.25g of melamine into an alumina crucible, placing the alumina crucible into a tube furnace, roasting the alumina crucible for 4 hours at 550 ℃ in a nitrogen atmosphere, and grinding the mixture to obtain uniform powder g-C3N4。
2) 2.5ml of nitric acid solution was added to 0.6g g-C3N4Heating and stirring for 3h in a water bath at the temperature of 80 ℃ to obtain a mixed solution.
3) Adding the mixed solution into a hydrothermal kettle, putting the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 10-12h at the temperature of 120-150 ℃ to obtain solid powder.
4) Putting the solid powder into an open evaporating dish, putting the evaporating dish into an oven, drying the evaporating dish for 10 to 12 hours at the temperature of between 80 and 100 ℃ in the air atmosphere to obtain a target product, namely the graphite-phase carbon nitride photocatalyst g-C with large specific surface area carbon deposition defects3N4(as ECNV-2.5).
(II) the result of the detection
XRD testing of the product ECNV-2.5 is shown in FIG. 1. from FIG. 1, it can be seen that the sample prepared has two diffraction peaks (13 ℃ and 27 ℃), which are typical of graphite phase carbon nitride, with the resulting pure g-C3N4Similarly.
The product ECNV-2.5 was subjected to nitrogen adsorption desorption test and the results are shown in FIG. 2, which shows a hysteresis loop indicating that ECNV-2.5 has a porous structure with a pore size distribution of 2-28nm, and the test results show that the obtained porous ECNV-2.5 has a pore size of 43m2Specific surface area in g.
The product ECNV-2.5 was tested by UV-vis, the results are shown in FIG. 3, which shows the comparison with pure g-C3N4The absorption edge of (a) is blue-shifted while figure 4 shows a band gap position of 2.85, indicating that the band gap is broadened, prolonging the lifetime of the photogenerated carriers and increasing the photocatalytic activity.
ECNV-2.5 was subjected to SEM test results as shown in (c) of FIG. 5-1, from which it was seen that ECNV-2.5 showed a layered, finer bulk polymer, which is an image of a typical exfoliated graphite phase carbon nitride. TEM image of ECNV-2.5, as shown in FIG. 5-2 (f), ECNV-2.5 has many small white spots, which are the holes produced in example 2.
The product ECNV-2.5 was XPS tested and the results of the allpass test are shown in FIG. 6. it can be seen from FIG. 6 that the sample ECNV-1.25 contains C, N and O elements, along with pure g-C3N4Similarly. The elemental fine spectra are shown in fig. 7 and 8, where the binding energy of both C and N elements is changed, thus illustrating the presence of carbon defects.
The ECNV-2.5 is subjected to EPR testing and the results are shown in FIG. 9. it is apparent from FIG. 9 that the unpaired electron in ECNV-2.5 is increased, indicating the occurrence of a defect, which is the carbon element.
(III) application
The prepared ECNV-2.5 photocatalyst is subjected to an isopropanol photocatalytic degradation experiment.
The test process is as follows: using 300W xenon lamp as light source, and mixing the prepared photocatalyst (ECNV-2.5) 0.1g and pure g-C3N4Placing in a 4cm container2In the glass tank, the glass tank loaded with the photocatalyst is placed into a 300ml reactor containing atmospheric pressure air, 5ul of isopropanol liquid is injected into the reactor, the system is kept stand for 3 hours to ensure that the system is in adsorption-desorption equilibrium, and then the isopropanol is degraded under the irradiation of visible light.
As shown in FIGS. 10 and 11, the lengths of the rectangles in the graph indicate the rate of acetone generation under visible light irradiation, and it can be seen that the graphite phase carbon nitride with carbon defects having a large specific surface area prepared in example 2 shows a very good photocatalytic activity, which reaches 46.76ppm/min, whereas the graphite phase carbon nitride prepared by the conventional method reaches 4.923 ppm/min.
Example 3 a graphite phase carbon nitride photocatalyst with large specific surface area carbon defects (nitric acid 3.75ml)
The preparation method comprises
1) 2.25g of melamine were added to an alumina crucible and placed in a tube furnace under nitrogen atmosphereRoasting at 550 deg.C for 4h, grinding to obtain uniform powder g-C3N4。
2) 3.75ml of nitric acid solution was added to 0.6g g-C3N4Heating and stirring for 3h in a water bath at the temperature of 80 ℃ to obtain a mixed solution.
3) Adding the mixed solution into a hydrothermal kettle, putting the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 10-12h at the temperature of 120-150 ℃ to obtain solid powder.
4) Putting the solid powder into an open evaporating dish, putting the evaporating dish into an oven, drying the evaporating dish for 10 to 12 hours at the temperature of between 80 and 100 ℃ in the air atmosphere to obtain a target product, namely the graphite-phase carbon nitride photocatalyst g-C with large specific surface area carbon deposition defects3N4(as ECNV-3.75).
(II) the result of the detection
XRD testing of the product ECNV-3.75 was performed as shown in FIG. 1. from FIG. 1, it can be seen that the sample prepared exhibited two diffraction peaks (13 ℃ and 27 ℃ C.), which are typical of graphite phase carbon nitride, with the resulting pure g-C3N4Similarly.
The product ECNV-3.75 was subjected to nitrogen adsorption desorption test, and the results are shown in FIG. 2, which shows a hysteresis loop indicating that ECNV-3.75 has a porous structure and a pore size distribution of 2-28nm, and the test results show that the obtained porous ECNV-3.75 has a pore size of 52m2Specific surface area in g.
The product ECNV-3.75 was tested by UV-vis, the results are shown in FIG. 3, which shows the comparison with pure g-C3N4The absorption edge of (a) is blue-shifted while figure 4 shows a band gap position of 2.86, indicating that the band gap is broadened, prolonging the lifetime of the photogenerated carriers and increasing the photocatalytic activity.
The obtained ECNV-3.75 was subjected to SEM test as shown in (d) of FIG. 5-1, together with pure g-C3N4Compared with the SEM image, ECNV-3.75 shows a loose, thin, cellular structure and a very porous structure on the surface.
(III) application
The g-CNA-3 photocatalyst prepared in this example 3 was subjected to an experiment for photocatalytic degradation of isopropanol.
Test procedureComprises the following steps: using 300W xenon lamp as light source, respectively adding 0.1g of photocatalyst (ECNV-3.75) and g-C prepared above3N4Placing in a 4cm container2In the glass tank, the glass tank loaded with the photocatalyst is placed into a 300ml reactor containing atmospheric pressure air, 5ul of isopropanol liquid is injected into the reactor, the system is kept stand for 3 hours to ensure that the system is in adsorption-desorption equilibrium, and then the isopropanol is degraded under the irradiation of visible light.
As shown in FIGS. 10 and 11, the lengths of the rectangles in the figure represent the rate of acetone generation under visible light irradiation, and it can be seen that the graphite-phase carbon nitride having a large specific surface area prepared in example 3 exhibits excellent photocatalytic activity, which is 30.789ppm/min, while the graphite-phase carbon nitride prepared by the conventional method is 4.923 ppm/min.
Claims (1)
1. A method for degrading isopropanol under visible light is characterized in that the method comprises the following steps of placing a graphite phase carbon nitride photocatalyst with carbon deposition defects on a large specific surface area in a closed space containing isopropanol gas under the irradiation of visible light for adsorption;
the preparation method of the graphite phase carbon nitride photocatalyst with the large specific surface area carbon deposition defects comprises the following steps:
1) adding 2.25g of melamine into an alumina crucible, placing the alumina crucible into a tube furnace, roasting the alumina crucible for 4 hours at 550 ℃ in a nitrogen atmosphere, and grinding the mixture to obtain uniform powder g-C3N4；
2) 2.5ml of nitric acid solution was added to 0.6g g-C3N4Heating and stirring for 3 hours in a water bath at the temperature of 80 ℃ to obtain a mixed solution;
3) adding the mixed solution into a hydrothermal kettle, putting the hydrothermal kettle into an oven, and carrying out hydrothermal reaction for 10-12h at the temperature of 120-;
4) and (3) putting the solid powder into an open evaporating dish, putting the evaporating dish into an oven, and drying the evaporating dish for 10-12h at the temperature of 80-100 ℃ in the air atmosphere to obtain the target product.
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