CN110371937B - Graphite phase carbon nitride energy band regulation and control method - Google Patents

Graphite phase carbon nitride energy band regulation and control method Download PDF

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CN110371937B
CN110371937B CN201910501882.2A CN201910501882A CN110371937B CN 110371937 B CN110371937 B CN 110371937B CN 201910501882 A CN201910501882 A CN 201910501882A CN 110371937 B CN110371937 B CN 110371937B
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carbon nitride
graphite
phase carbon
energy band
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沈少华
赵大明
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Xian Jiaotong University
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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
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Abstract

The invention discloses a method for regulating and controlling a graphite-phase carbon nitride energy band, which is to regulate and control g-C3N4With NaBH4According to the mass ratio (1-5): 1, then calcining for 0.5-2 h at 300-600 ℃, and enabling NaBH to be at 300-600 DEG C4At the thermal decomposition temperature, decomposition produces active B3+And activity H‑In which B is3+By substitution of g-C3N4C in (1) into g-C3N4Namely introducing B doping; h‑Has extremely high reducibility, and makes g-C3N4Part of N in NH3Form deletion, i.e. introduction of N defects, using B doping and N defects reduces g-C3N4To reduce the conduction and valence band positions of3N4The forbidden band width of the crystal is increased, and the introduction of B doping and N defects can be mutually promoted to reach a high introduction density to cause g-C3N4A large change in the electronic structure, thereby modulating the g-C significantly3N4The method is simple, has wide regulation range of the energy band of the graphite-phase carbon nitride, strong controllability, good repeatability, cheap raw materials, wide sources, greenness, safety and environmental protection, improves the production efficiency, reduces the production cost, and is suitable for large-scale production.

Description

Graphite phase carbon nitride energy band regulation and control method
Technical Field
The invention belongs to the field of graphite phase carbon nitride materials, and particularly relates to a method for regulating and controlling a graphite phase carbon nitride energy band.
Background
Graphite phase carbon nitride (g-C)3N4) The material is a novel non-metal two-dimensional material, the energy band structure of the material is suitable for two key half reaction steps of hydrogen production and oxygen production in photocatalytic decomposition water, and the material has the advantages of rich precursor source, simple synthesis method, good thermal stability, no heavy metal pollution and the like, so the material is generally regarded as a photocatalytic material with wide application prospect and has important research value in the fields of photocatalytic decomposition water, artificial photosynthesis, degradation of organic pollutants, gas oxidation/reduction and the like.
However, at present g-C3N4The photocatalytic reaction still faces the trouble of wider forbidden band width. g-C synthesized by traditional pyrolysis method3N4Typically have a wide forbidden band width (2.70eV) and absorb only a small fraction of the short wavelength light in the visible. How to regulate and control the energy band structure of the material, thereby widening the absorption capacity of visible light and even improving the oxidation/reduction potential, becomes one of the research hotspots in the field. The processes currently employed generally involve multi-step operations and harsh reaction conditionsThe experimental procedure is dangerous and difficult to apply on a large scale (e.g. high temperature reduction with pure hydrogen or ammonia, adv. mater.2014,26, 8046-. More importantly, due to g-C3N4Stable chemical structure, the current method cannot modulate g-C greatly3N4The band structure (adv. Funct. Mater.2015,25,6885-3N4Photocatalytic oxidation/reduction performance.
Disclosure of Invention
The invention aims to provide a graphite phase carbon nitride energy band regulation and control method, which aims to solve the technical problems that the graphite phase carbon nitride energy band regulation and control method in the prior art is high in operation difficulty, high in potential safety hazard, small in regulation range, difficult to improve oxidation/reduction potential while reducing the forbidden band width, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphite phase carbon nitride energy band regulation and control method comprises the following steps:
step 1) regulating g-C3N4With NaBH4According to the mass ratio (1-5): 1, uniformly mixing to obtain a mixture A;
and 2) calcining the mixture A in an inert gas atmosphere to complete energy band regulation of the graphite-phase carbon nitride, wherein the calcining temperature is 300-600 ℃, and the calcining time is 0.5-2 h.
Further, calcining the mixture A in an inert gas atmosphere to obtain a mixture B, washing the mixture B by centrifugal water, drying the mixture B in a vacuum oven, and drying to obtain the graphite-phase carbon nitride with the regulated energy band.
Furthermore, the graphite-phase carbon nitride obtained by the method has a forbidden band width of 2.66-1.40 eV, a conduction band potential of-0.95-1.10V vs standard hydrogen electrode, and a valence band potential of 1.71-2.50V vs standard hydrogen electrode.
Further, centrifuging and washing for 3-6 times, wherein the centrifuging speed is 6000-15000 r/min, and the centrifuging time is 5-15 min.
Further, g-C3N4With NaBH4According to the mass ratio (1-5): 1, placing the mixture in a mortar, and grinding, stirring and mixing for 5-30 min to obtain a uniform mixture A.
Further, in the step 2), the mixture A is placed into a crucible and then is placed into a tubular furnace, inert gas is used as protective gas in the tubular furnace, the tubular furnace is heated from room temperature to the calcination temperature of 300-600 ℃ at the heating rate of 10-30 ℃/s, then calcination is carried out for 0.5-2 h at the calcination temperature of 300-600 ℃, and then natural cooling is carried out to the room temperature, so that the energy band regulation of the graphite-phase carbon nitride can be completed.
Further, after the mixture A is placed into a crucible and then is placed into a tube furnace, the tube furnace is repeatedly vacuumized and protective gas is introduced for 3-5 times.
Further, nitrogen or argon is used as the inert gas.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a method for regulating and controlling a graphite-phase carbon nitride energy band, which is characterized in that g-C to be regulated and controlled3N4With NaBH4According to the mass ratio (1-5): 1, evenly mixing to obtain a mixture A, then calcining for 0.5-2 h at 300-600 ℃, and enabling NaBH to be at 300-600 DEG C4At the thermal decomposition temperature, decomposition produces active B3+And activity H-In which B is3+By substitution of g-C3N4C in (1) into g-C3N4Namely introducing B doping; h-Has extremely high reducibility, and makes g-C3N4Part of N in NH3Form deletion, i.e. introduction of N defects, using B doping and N defects reduces g-C3N4To reduce the conduction and valence band positions of3N4The forbidden band width of the crystal is increased, and the introduction of B doping and N defects can be mutually promoted to reach a high introduction density to cause g-C3N4A large change in the electronic structure, thereby modulating the g-C significantly3N4The method has the advantages of simple structure, wide regulation range of the energy band of the graphite-phase carbon nitride, strong controllability, good repeatability, cheap and wide raw materials, and environmental friendlinessThe method is safe and environment-friendly, improves the production efficiency, reduces the production cost and is suitable for large-scale production. The invention realizes g-C by using a safe and easy-to-operate method3N4Wide modulation of forbidden band width, conduction band and valence band position. Regulated g-C3N4Has good dispersibility and can be stored stably. The method has no organic solvent and heavy metal chemical reagent in the reaction process, not only can effectively avoid the problem of environmental pollution, but also can bring regulated g-C3N4The non-toxic characteristic makes it widely used in the fields of photocatalytic water decomposition, artificial photosynthesis, organic pollutant degradation, gas oxidation/reduction, etc. The whole preparation process is simple to operate.
Further, rapid temperature increases can cause NaBH to occur4Directly reaching thermal decomposition temperature, thereby decomposing to generate active B3+And activity H-。
Drawings
FIG. 1a shows the g-C after regulation in example 1 of the present invention3N4A light absorption spectrum of (a); FIG. 1b is a diagram of an energy spectrum obtained by Kubelka-Munk transformation of a light absorption spectrum; FIG. 1C shows the regulated g-C obtained in example 13N4X-ray photoelectron spectroscopy; FIG. 1d shows the regulated g-C obtained in example 13N4Energy band structure diagram of (1).
FIG. 2a shows g-C after modulation in example 2 of the present invention3N4A light absorption spectrum of (a); FIG. 2b is a diagram of an energy spectrum obtained by Kubelka-Munk transform of a light absorption spectrum; FIG. 2C shows the regulated g-C obtained in example 23N4X-ray photoelectron spectroscopy; FIG. 2d shows the regulated g-C obtained in example 23N4Energy band structure diagram of (1).
FIG. 3a shows the g-C after modulation in example 3 of the present invention3N4A light absorption spectrum of (a); FIG. 3b is a diagram of an energy spectrum obtained by Kubelka-Munk transform of a light absorption spectrum; FIG. 3C shows the regulated g-C obtained in example 33N4X-ray photoelectron spectroscopy; FIG. 3d shows the regulated g-C obtained in example 33N4Energy band structure diagram of (1).
FIG. 4a shows an embodiment of the present invention4 regulated g-C3N4A light absorption spectrum of (a); FIG. 4b is a diagram of an energy spectrum obtained by Kubelka-Munk transform of a light absorption spectrum; FIG. 4C shows the regulated g-C obtained in example 43N4X-ray photoelectron spectroscopy; FIG. 4d shows the regulated g-C obtained in example 43N4Energy band structure diagram of (1).
FIG. 5a shows the g-C after modulation in example 5 of the present invention3N4A light absorption spectrum of (a); FIG. 5b is a diagram of an energy spectrum obtained by Kubelka-Munk transform of a light absorption spectrum; FIG. 5C shows the regulated g-C obtained in example 53N4X-ray photoelectron spectroscopy; FIG. 1d shows the regulated g-C obtained in example 53N4Energy band structure diagram of (1).
FIG. 6a shows g-C to be regulated3N4A light absorption spectrum of (a); FIG. 6b is a diagram of an energy spectrum obtained by Kubelka-Munk transform of a light absorption spectrum; FIG. 6C shows g-C to be regulated3N4X-ray photoelectron spectroscopy; FIG. 6d shows g-C to be regulated3N4Complete band structure diagram of (2).
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
the invention aims to provide a non-metallic two-dimensional material graphite phase carbon nitride (g-C)3N4) Provides an effective energy band regulation method, which carries out NaBH on graphite phase carbon nitride4The heat treatment method can obtain g-C with good dispersibility, stable storage, wide modulation of forbidden band width and energy band position3N4. The invention has short reaction time, less raw material consumption and low reaction temperature, improves the production efficiency, reduces the production cost and overcomes the defects of the prior g-C3N4The problems of high operation difficulty, high potential safety hazard and the like in the regulation and control of the energy band structure are solved, and the large-scale preparation and the practical application are facilitated.
The technical scheme of the invention comprises the step of3N4Boron doping and nitrogen defects are introduced into the structure at the same time, impurity ions are removed, and the boron doping and the nitrogen defects can be removed by utilizing NaBH in a rapid heating tube furnace4Heat treatment to simultaneously introduce g-C3N4In the structure, centrifugal washing and vacuum drying are combined to obtain g-C with the forbidden band width and the positions of the conduction band and the valence band being greatly adjusted3N4。
The preferable specific technical scheme of the invention specifically comprises the following reaction steps:
step 1) regulating g-C3N4With NaBH4According to the mass ratio (1-5): 1, uniformly mixing to obtain a mixture A;
specifically, g-C3N4With NaBH4According to the mass ratio (1-5): 1, placing the mixture in a mortar, grinding, stirring and mixing for 5-30 min to obtain uniform g-C3N4-NaBH4And (3) mixing.
Step 2), fully calcining the mixture A in an inert gas atmosphere to obtain a calcined mixture B, and thus finishing the energy band regulation of the graphite-phase carbon nitride;
specifically, the crucible filled with the mixture A is placed into a tubular furnace, and inert gas in the tubular furnace is used as protective gas, wherein the inert gas is nitrogen or argon; and (3) repeatedly vacuumizing the inside of the tube furnace before calcination, introducing protective gas for 3-5 times, and removing air in the tube furnace to ensure that the tube furnace is in an inert gas protective atmosphere. Heating the tube furnace from room temperature to a calcination temperature of 300-600 ℃ at a heating rate of 10-30 ℃/s, and calcining at the calcination temperature of 300-600 ℃ for 0.5-2 h to obtain g-C3N4Carrying out full reduction reaction, and then naturally cooling to room temperature;
step 3), removing impurities from the mixture B to obtain regulated g-C3N4And obtaining the graphite-phase carbon nitride with the energy band regulated and controlled.
Specifically, the mixture B is washed by centrifugal water for 3-6 times, the centrifugal rotating speed is 6000-15000 r/min, the single centrifugation time is 5-15 min, and the aim of centrifugal water washing is to remove Na in the mixture B; then drying the residual product in a vacuum oven at the temperature of 60-100 ℃ for 6-20 h to obtain the g-C with the greatly modulated target product energy band structure3N4Regulated g-C3N4The forbidden band width range is 2.66-1.40 eV, and the conduction band potential range is-0.95-1.10V vs standard hydrogen electrode, and the valence band potential range is 1.71-2.50V vs standard hydrogen electrode.
FIG. 6a is a light absorption spectrum of a material, as shown in FIG. 6; fig. 6b is the energy spectrum obtained by Kubelka-Munk transform in fig. 6a, and the forbidden bandwidth of the material can be known from fig. 6 b; FIG. 6c is an X-ray photoelectron spectrum of the material, from which FIG. 6c the valence band position of the material can be derived; according to the forbidden band width and the valence band position, the position of the conduction band can be known, and the complete energy band structure diagram of the material, namely the diagram of fig. 6, can be obtained through standard potential correction.
The technical solution of the present invention will be described in detail with reference to the accompanying drawings and some preferred embodiments of the present invention.
Example 1
1) 400mg of g-C to be regulated3N4With 100mg NaBH4Mixing thoroughly for 15min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing and introducing the protective gas for 5 times before calcining, wherein the air flow velocity is 50 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 300 ℃ at the heating rate of 10 ℃/s, then the mixture is calcined for 2 hours at the calcining temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging the mixture B, washing with water for 5 times at 6000r/min for 10min, collecting solid, drying at 60 deg.C for 15 hr in a vacuum oven to obtain target product (regulated g-C)3N4. Regulated g-C3N4The performance parameters are shown in fig. 1 d.
Example 2
1) 400mg of g-C to be regulated3N4With 100mg NaBH4Mixing thoroughly for 10min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing and introducing the protective gas for 5 times before calcining, wherein the air flow velocity is 80 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 350 ℃ at the heating rate of 10 ℃/s, then the mixture is calcined for 1.5h at the calcining temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging the mixture B, washing with water for 4 times at 8000r/min for 15min, collecting solid, and drying at 60 deg.C for 10 hr in a vacuum oven to obtain target product (regulated g-C)3N4. Regulated g-C3N4The performance parameters are shown in fig. 2 d.
Example 3
1) 400mg of g-C to be regulated3N4With 150mg NaBH4Mixing thoroughly for 15min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, and introducing the protective gas for 4 times, wherein the air flow velocity is 100 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 400 ℃ at the temperature increase rate of 15 ℃/s, then the mixture is calcined for 1 hour at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 4 times at 10000r/min for 10min, collecting solid, and drying at 70 deg.C for 15 hr in a vacuum oven to obtain target product (regulated g-C)3N4. Regulated g-C3N4The performance parameters are shown in fig. 3 d.
Example 4
1) 400mg of g-C to be regulated3N4With 200mg NaBH4Mixing thoroughly for 15min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 150 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 450 ℃ at the temperature increase rate of 15 ℃/s, then the mixture is calcined for 1 hour at the calcining temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 3 times at 10000r/min for 10min, collecting solid, and drying at 70 deg.C for 10h in a vacuum oven to obtain target product (regulated g-C)3N4. Regulated g-C3N4The performance parameters are shown in fig. 4 d.
Example 5
1) 400mg of g-C to be regulated3N4With 200mg NaBH4Mixing thoroughly for 20min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 150 mL/min; during calcination, the tubular furnace is heated from room temperature to the calcination temperature of 500 ℃ at the heating rate of 20 ℃/s, then the mixture is calcined for 1 hour at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 3 times at 12000r/min for 10min, collecting solid, and drying at 80 deg.C for 10 hr in a vacuum oven to obtain target product (regulated g-C)3N4. Regulated g-C3N4The performance parameters are shown in fig. 5 d.
Example 6
1) 400mg of g-C to be regulated3N4With 300mg NaBH4Mixing thoroughly for 25min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 200 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 550 ℃ at the temperature increase rate of 20 ℃/s, then the mixture is calcined for 0.5h at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging mixture B, washing with water for 4 times at 12000r/min for 5min, collecting solid in vacuum oven to obtain solidDrying at 80 deg.C for 8h to obtain target product, i.e. regulated g-C3N4。
Example 7
1) 400mg of g-C to be regulated3N4With 400mg NaBH4Mixing thoroughly for 30min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 250 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 550 ℃ at the temperature increase rate of 25 ℃/s, then the mixture is calcined for 1 hour at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 3 times at 12000r/min for 5min, collecting solid, and drying at 80 deg.C for 6 hr in a vacuum oven to obtain target product (regulated g-C)3N4。
Example 8
1) 400mg of g-C to be regulated3N4With 80mg NaBH4Mixing thoroughly for 5min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 250 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 600 ℃ at the temperature increase rate of 30 ℃/s, then the mixture is calcined for 1 hour at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging the mixture B, washing with water for 3 times at 15000r/min for 5min, collecting solid, drying in vacuum oven at 80 deg.C for 6 hr to obtain target product, i.e. regulated g-C3N4。
Example 9
1) 400mg of g-C to be regulated3N4With 350mg NaBH4Mixing thoroughly for 30min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 250 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to the calcination temperature of 580 ℃ at the temperature increase rate of 25 ℃/s, then the mixture is calcined for 1 hour at the calcination temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 3 times at 13000r/min for 5min, collecting the solid, drying in a vacuum oven at 90 deg.C for 6h to obtain the target product, i.e. regulated g-C3N4。
Example 10
1) 400mg of g-C to be regulated3N4With 250mg NaBH4Mixing thoroughly for 20min to obtain uniform g-C3N4-NaBH4A mixture A;
2) placing the crucible filled with the mixture A into a rapid heating tubular furnace, using nitrogen as a protective gas in the tubular furnace, repeatedly vacuumizing before calcining, introducing the protective gas for 3 times, and controlling the air flow rate to be 250 mL/min; during calcination, the temperature of the tubular furnace is increased from room temperature to 300 ℃ at the heating rate of 10 ℃/s, then the mixture is calcined for 1h at the calcining temperature, and then the mixture is naturally cooled to the room temperature to obtain a mixture B;
3) centrifuging and washing the mixture B for 3 times at 14000r/min for 5min, collecting solid, and drying at 70 deg.C for 6 hr in a vacuum oven to obtain target product (regulated g-C)3N4。
The invention is realized by regulating g-C3N4With NaBH4According to the mass ratio (1-5): 1, evenly mixing to obtain a mixture A, then calcining for 0.5-2 h at 300-600 ℃, and enabling NaBH to be at 300-600 DEG C4At the thermal decomposition temperature, decomposition produces active B3+And activity H-In which B is3+By substitution of g-C3N4C in (1) into g-C3N4Namely introducing B doping; h-Has extremely high reducibility, and makes g-C3N4In (1)Part of N being NH3Form deletion, i.e. introduction of N defects, using B doping and N defects reduces g-C3N4To reduce the conduction and valence band positions of3N4The forbidden band width of the crystal is increased, and the introduction of B doping and N defects can be mutually promoted to reach a high introduction density to cause g-C3N4A large change in the electronic structure, thereby modulating the g-C significantly3N4The method is simple, has wide regulation range of the energy band of the graphite-phase carbon nitride, strong controllability, good repeatability, cheap raw materials, wide sources, greenness, safety and environmental protection, improves the production efficiency, reduces the production cost, and is suitable for large-scale production. The invention realizes g-C by using a safe and easy-to-operate method3N4Wide modulation of forbidden band width, conduction band and valence band position. Regulated g-C3N4Has good dispersibility and can be stored stably. The method has no organic solvent and heavy metal chemical reagent in the reaction process, not only can effectively avoid the problem of environmental pollution, but also can bring regulated g-C3N4The non-toxic characteristic makes it widely used in the fields of photocatalytic water decomposition, artificial photosynthesis, organic pollutant degradation, gas oxidation/reduction, etc. The whole preparation process is simple to operate.
Conditioned g-C obtained according to examples 1 to 53N4Performance parameters, as can be seen from the band structure diagrams of FIGS. 1-5, g-C modulated by the method of the invention3N4The forbidden band width and the energy band position are ideally and greatly adjusted, the forbidden band width range of the graphite-phase carbon nitride obtained by the method is 2.66-1.40 eV, the conduction band potential range is-0.95-1.10V vs standard hydrogen electrode, the valence band potential range is 1.71-2.50V vs standard hydrogen electrode, and the g-C before adjustment is opposite to that of the standard hydrogen electrode3N4There is a large variation.
It should be noted that the above description and the preferred embodiments are not to be construed as limiting the design concept of the present invention. Those skilled in the art can modify the technical idea of the present invention in various forms, and such modifications and changes are understood to fall within the scope of the present invention.

Claims (5)

1. A graphite phase carbon nitride energy band regulation and control method is characterized by comprising the following steps:
step 1) regulating g-C3N4With NaBH4According to the mass ratio (1-5): 1, uniformly mixing to obtain a mixture A;
step 2), calcining the mixture A in an inert gas atmosphere to complete energy band regulation of graphite-phase carbon nitride, wherein the calcining temperature is 300-600 ℃, and the calcining time is 0.5-2 h, specifically, calcining the mixture A in the inert gas atmosphere to obtain a mixture B, washing the mixture B by centrifugal water, drying the mixture B in a vacuum oven to obtain the graphite-phase carbon nitride with the regulated energy band, putting the mixture A into a crucible, putting the mixture A into a tubular furnace, introducing inert gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to the calcining temperature of 300-600 ℃ at the heating rate of 10-30 ℃/s, calcining at the calcining temperature of 300-600 ℃ for 0.5-2 h, and naturally cooling to room temperature to complete the energy band regulation of the graphite-phase carbon nitride; and introducing B doping and N defects into a molecular structure of the graphite-phase carbon nitride, wherein the obtained graphite-phase carbon nitride has a forbidden band width of 2.39-1.40 eV, a conduction band potential range of-0.42-1.10 Vvs standard hydrogen electrode and a valence band potential range of 1.97-2.50 Vvs standard hydrogen electrode.
2. The method for regulating the energy band of graphite-phase carbon nitride according to claim 1, wherein the washing is performed 3-6 times by centrifugation, the centrifugation speed is 6000-15000 r/min, and the centrifugation time is 5-15 min.
3. The method for regulating the energy band of graphite-phase carbon nitride according to claim 1, wherein g-C is added3N4With NaBH4According to the mass ratio (1-5): 1, placing the mixture in a mortar, and grinding, stirring and mixing for 5-30 min to obtain a uniform mixture A.
4. The method for regulating and controlling the energy band of graphite-phase carbon nitride according to claim 3, wherein the mixture A is placed in a crucible, then is placed in a tube furnace, and then is subjected to repeated vacuum pumping and protective gas introduction for 3-5 times.
5. The method for regulating the energy band of graphite-phase carbon nitride according to claim 1, wherein the inert gas is nitrogen or argon.
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