CN110371937A - A kind of graphite phase carbon nitride band engineering method - Google Patents
A kind of graphite phase carbon nitride band engineering method Download PDFInfo
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- CN110371937A CN110371937A CN201910501882.2A CN201910501882A CN110371937A CN 110371937 A CN110371937 A CN 110371937A CN 201910501882 A CN201910501882 A CN 201910501882A CN 110371937 A CN110371937 A CN 110371937A
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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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- 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
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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 kind of graphite phase carbon nitride band engineering methods, will g-C be regulated and controled3N4With NaBH4According to mass ratio (1~5): 1 is uniformly mixed, and 0.5~2h is then calcined at 300~600 DEG C, makes NaBH at 300~600 DEG C4In thermal decomposition temperature, decomposes and generate activity B3+With active H‑, wherein B3+By replacing g-C3N4In C and enter g-C3N4, i.e. introducing B doping;H‑With high reproducibility, make g-C3N4In part N with NH3Form missing, i.e., introducing N defect, using B doping and N defect can reduce g-C3N4Conduction band and valence band location, to reduce g-C3N4Forbidden bandwidth, while B doping and the introducing of N defect can mutually promote, and reach a very high introducing density, cause g-C3N4The substantially change of electronic structure, thus substantially modulation g-C3N4Band structure, the method for the present invention is simple, wide to the band engineering range of graphite phase carbon nitride, and controllability is strong, and reproducible, raw material is cheap and from a wealth of sources, and green safe environmental protection improves production efficiency, reduces production cost, is suitble to large-scale production.
Description
Technical field
The invention belongs to graphite phase carbon nitride Material Fields, and in particular to a kind of graphite phase carbon nitride band engineering method.
Background technique
Graphite phase carbon nitride (g-C3N4) it is a kind of novel metalloid two-dimensional material, band structure is suitable for photocatalysis
Production hydrogen and the crucial half-reaction steps of production oxygen two in decomposition water, while it is simple, hot to have both presoma abundance, synthetic method
Have good stability, heavy metal free pollution many advantages, such as, therefore be generally considered as the catalysis material with broad prospect of application,
There is important research in fields such as photochemical catalyzing, artificial photosynthesis, organic pollutant degradation and gas oxidation/reductions
Value.
However current g-C3N4The wider puzzlement of forbidden bandwidth is still suffered from light-catalyzed reaction.Using conventional pyrolytic method
The g-C of synthesis3N4Usually there is wider forbidden bandwidth (2.70eV), be only capable of absorbing very least a portion of short-wavelength light in visible light.
How its band structure is regulated and controled, and then the absorbability for widening visible light even improves oxidation/reduction current potential, becomes this
One of the research hotspot in field.Currently used method is usually directed to the reaction condition of many more manipulations and harshness, experimentation
It is dangerous and be difficult to large-scale application (as using pure hydrogen or ammonia high temperature reduction, Adv.Mater.2014,26,8046-8052;
Adv.Funct.Mater.2015,25,6885-6892).Importantly, due to g-C3N4Stable chemical structure, current
Method cannot substantially modulation g-C3N4Band structure (Adv.Funct.Mater.2015,25,6885-6892;
Appl.Catal.B 2019,240,64-71), such band engineering method is difficult really effectively to enhance g-C3N4Light urge
Change oxidation/reduction performance.
Summary of the invention
The purpose of the present invention is to provide a kind of graphite phase carbon nitride band engineering methods, to solve graphite in the prior art
Phase carbon nitride band engineering method operation difficulty is big, security risk is high, modulation range is small, is difficult to while reducing forbidden bandwidth
Improve the technical problems such as oxidation/reduction current potential.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of graphite phase carbon nitride band engineering method, comprising the following steps:
Step 1), will g-C be regulated and controled3N4With NaBH4According to mass ratio (1~5): 1 be uniformly mixed obtain mixture A;
Step 2) carries out mixture A to calcine the energy band tune that graphite phase carbon nitride can be completed under atmosphere of inert gases
Control, calcination temperature are 300~600 DEG C, and calcination time is 0.5~2h.
Further, mixture B is obtained after mixture A being calcined under atmosphere of inert gases, and mixture B is passed through
Centrifugation washing is placed on vacuum drying oven drying, and the graphite phase carbon nitride after band engineering can be obtained after dry.
It further, is 2.66~1.40eV according to the forbidden bandwidth range of graphite phase carbon nitride obtained by the above method,
Conduction band potential range is -0.95~1.10V vs standard hydrogen electrode, and valence band potential range is 1.71~2.50V vs standard hydrogen electricity
Pole.
Further, centrifugation washing 3~6 times, centrifugal rotational speed be 6000~15000r/min, centrifugation time be 5~
15min。
Further, by g-C3N4With NaBH4According to mass ratio (1~5): 1 is placed in mortar, is stirred 5 by grinding
Uniform mixture A can be obtained in~30min.
Further, in step 2), mixture A is put into after crucible and is put into togerther in tube furnace, the inertia into tube furnace
Gas rises to the heating rate of 10~30 DEG C/s 300~600 DEG C of calcining temperature as protective gas, by tube furnace from room temperature
Degree, then 0.5~2h is calcined under 300~600 DEG C of calcination temperature, then graphite-phase nitridation can be completed in cooled to room temperature
The band engineering of carbon.
Further, mixture A is put into after crucible to be put into togerther after tube furnace and tube furnace is vacuumized repeatedly-led to
Protection gas 3~5 times.
Further, inert gas uses nitrogen or argon gas.
Compared with prior art, the invention has the following beneficial technical effects:
A kind of graphite phase carbon nitride band engineering method of the present invention, by will g-C be regulated and controled3N4With NaBH4According to mass ratio
(1~5): 1 be uniformly mixed obtain mixture A, then at 300~600 DEG C calcine 0.5~2h, make at 300~600 DEG C
NaBH4In thermal decomposition temperature, decomposes and generate activity B3+With active H-, wherein B3+By replacing g-C3N4In C and enter g-
C3N4, i.e. introducing B doping;H-With high reproducibility, make g-C3N4In part N with NH3Form missing, i.e., introducing N lack
It falls into, g-C can be reduced using B doping and N defect3N4Conduction band and valence band location, to reduce g-C3N4Forbidden bandwidth, while B
Doping and the introducing of N defect can mutually promote, and reach a very high introducing density, cause g-C3N4Electronic structure is substantially
Change, thus substantially modulation g-C3N4Band structure, the method for the present invention is simple, wide to the band engineering range of graphite phase carbon nitride,
Controllability is strong, reproducible, and raw material is cheap and from a wealth of sources, and green safe environmental protection improves production efficiency, reduces and be produced into
This, is suitble to large-scale production.The present invention realizes g-C using the easily operated method of safety3N4Forbidden bandwidth, conduction band and valence band
The substantially modulation of position.The g-C that band engineering is crossed3N4Good dispersion, it is storage-stable.This method is during the reaction without organic
Solvent and heavy metal chemical reagent participate in, and problem of environmental pollution can not only be effectively avoided, simultaneously because the g-C that band engineering is crossed3N4
Nontoxic characteristic can be widely used in photochemical catalyzing, artificial photosynthesis, organic pollutant degradation and gas oxygen
The fields such as change/reduction.Whole preparation process of the invention is easy to operate.
Further, NaBH can be made by being rapidly heated4Thermal decomposition temperature is directly arrived at, generates activity B to decompose3+And activity
H-。
Detailed description of the invention
Fig. 1 a is the g-C after regulating and controlling in the embodiment of the present invention 13N4Light absorption spectrogram;Fig. 1 b is optical absorption spectra process
The energy spectrum diagram that Kubelka-Munk is converted;Fig. 1 c is g-C after the regulation that embodiment 1 obtains3N4X-ray photoelectron spectroscopy;
Fig. 1 d is g-C after the regulation that embodiment 1 obtains3N4Band structure figure.
Fig. 2 a is the g-C after regulating and controlling in the embodiment of the present invention 23N4Light absorption spectrogram;Fig. 2 b is optical absorption spectra process
The energy spectrum diagram that Kubelka-Munk is converted;Fig. 2 c is g-C after the regulation that embodiment 2 obtains3N4X-ray photoelectron spectroscopy;
Fig. 2 d is g-C after the regulation that embodiment 2 obtains3N4Band structure figure.
Fig. 3 a is the g-C after regulating and controlling in the embodiment of the present invention 33N4Light absorption spectrogram;Fig. 3 b is optical absorption spectra process
The energy spectrum diagram that Kubelka-Munk is converted;Fig. 3 c is g-C after the regulation that embodiment 3 obtains3N4X-ray photoelectron spectroscopy;
Fig. 3 d is g-C after the regulation that embodiment 3 obtains3N4Band structure figure.
Fig. 4 a is the g-C after regulating and controlling in the embodiment of the present invention 43N4Light absorption spectrogram;Fig. 4 b is optical absorption spectra process
The energy spectrum diagram that Kubelka-Munk is converted;Fig. 4 c is g-C after the regulation that embodiment 4 obtains3N4X-ray photoelectron spectroscopy;
Fig. 4 d is g-C after the regulation that embodiment 4 obtains3N4Band structure figure.
Fig. 5 a is the g-C after regulating and controlling in the embodiment of the present invention 53N4Light absorption spectrogram;Fig. 5 b is optical absorption spectra process
The energy spectrum diagram that Kubelka-Munk is converted;Fig. 5 c is g-C after the regulation that embodiment 5 obtains3N4X-ray photoelectron spectroscopy;
Fig. 1 d is g-C after the regulation that embodiment 5 obtains3N4Band structure figure.
Fig. 6 a is g-C to be regulated and controled3N4Light absorption spectrogram;Fig. 6 b is that optical absorption spectra converts to obtain by Kubelka-Munk
Energy spectrum diagram;Fig. 6 c is g-C to be regulated and controled3N4X-ray photoelectron spectroscopy;Fig. 6 d is g-C to be regulated and controled3N4Complete band structure
Figure.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
The present invention is directed to be nonmetallic two-dimensional material graphite phase carbon nitride (g-C3N4) a kind of effective band engineering side is provided
Method, by carrying out NaBH to graphite phase carbon nitride4Heat treating process obtains good dispersion, storage-stable, forbidden bandwidth and energy band
The g-C of position substantially modulation3N4.The experiment condition that reaction time of the invention is short, raw material usage is few, reaction temperature is low improves life
It produces efficiency, reduce production cost, overcome previous g-C3N4Operation difficulty present in band structure regulation is big, security risk is high
The problems such as, it is conducive to prepare with scale and practical application.
Technical solution of the present invention is included in g-C3N4Boron doping and nitrogen defect and foreign ion are introduced in structure simultaneously
Removal, boron doping and nitrogen defect can be by utilizing NaBH being rapidly heated in tube furnace4Heat treatment comes while being introduced into g-C3N4
In structure, in conjunction with centrifugation washing, vacuum drying, the g-C of forbidden bandwidth, conduction band and valence band location substantially modulation is obtained3N4。
Currently preferred specific technical solution specifically includes following reaction step:
Step 1), will g-C be regulated and controled3N4With NaBH4According to mass ratio (1~5): 1 be uniformly mixed obtain mixture A;
Specifically, by g-C3N4With NaBH4According to mass ratio (1~5): 1 is placed in mortar, and grinding is stirred 5~
30min obtains uniform g-C3N4-NaBH4Mixture.
Step 2) carries out mixture A fully calcined to obtain calcined mixture B under atmosphere of inert gases
Complete the band engineering of graphite phase carbon nitride;
To be specifically put into tube furnace equipped with the crucible of mixture A, into tube furnace inert gas as protective gas,
Specific inert gas uses nitrogen or argon gas;To being vacuumized-being led to protection gas 3~5 times in tube furnace repeatedly before calcining, exclude
Air in tube furnace, it is ensured that tube furnace is inert gas shielding atmosphere.By tube furnace with the heating rate of 10~30 DEG C/s from
Room temperature rises to 300~600 DEG C of calcination temperature, then 0.5~2h is calcined under 300~600 DEG C of calcination temperature, makes g-C3N4Hair
Abundant reduction reaction is given birth to, then cooled to room temperature;
Step 3), by can be obtained after mixture B impurity elimination regulation after g-C3N4, graphite after band engineering can be obtained
Phase carbon nitride.
Specifically by mixture B by centrifugation washing 3~6 times, centrifugal rotational speed is 6000~15000r/min, single spin
Time is 5~15min, is the Na removed in mixture B using centrifugation washing purpose;Then by resultant product in vacuum drying oven
With the dry 6~20h of 60~100 DEG C of temperature, obtains target product band structure and obtain the g-C of substantially modulation3N4, after regulation
g-C3N4Forbidden bandwidth range be 2.66~1.40eV, conduction band potential range be -0.95~1.10V vs standard hydrogen electrode, valence
Band potential range is 1.71~2.50V vs standard hydrogen electrode.
As shown in fig. 6, Fig. 6 a is the optical absorption spectra of material;Fig. 6 b is the energy that Fig. 6 a passes through that Kubelka-Munk is converted
Spectrum, can learn the forbidden bandwidth of material from Fig. 6 b;Fig. 6 c is the x-ray photoelectron spectroscopy of material, can be obtained from Fig. 6 c
Know the valence band location of material;According to forbidden bandwidth and valence band location, so that it may know conduction band positions, is corrected by normal potential,
It can be obtained by the complete band structure figure of material, i.e. Fig. 6.
Technical solution of the present invention is made below in conjunction with attached drawing and several preferred embodiments of the present invention further detailed
Explanation.
Embodiment 1
1) by 400mg g-C to be regulated and controled3N4With 100mg NaBH4It is sufficiently mixed 15min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 5 times, air velocity 50mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 10 DEG C/s
300 DEG C of calcination temperature is risen to from room temperature, then calcines 2h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 5 times, centrifugal rotational speed 6000r/min, the single spin time is 10min, is then received
Collect solid with the dry 15h of 60 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4.G- after regulation
C3N4Performance parameter is as shown in Figure 1 d.
Embodiment 2
1) by 400mg g-C to be regulated and controled3N4With 100mg NaBH4It is sufficiently mixed 10min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 5 times, air velocity 80mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 10 DEG C/s
350 DEG C of calcination temperature is risen to from room temperature, then calcines 1.5h at calcination temperatures, and then cooled to room temperature obtains mixture
B;
3) by mixture B centrifugation washing 4 times, centrifugal rotational speed 8000r/min, the single spin time is 15min, is then received
Collect solid with the dry 10h of 60 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4.G- after regulation
C3N4Performance parameter is as shown in Figure 2 d.
Embodiment 3
1) by 400mg g-C to be regulated and controled3N4With 150mg NaBH4It is sufficiently mixed 15min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 4 times, air velocity 100mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 15 DEG C/s
400 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 4 times, centrifugal rotational speed 10000r/min, the single spin time is 10min, then
Solid is collected with the dry 15h of 70 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4.After regulation
g-C3N4Performance parameter is as shown in Figure 3d.
Embodiment 4
1) by 400mg g-C to be regulated and controled3N4With 200mg NaBH4It is sufficiently mixed 15min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 150mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 15 DEG C/s
450 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 10000r/min, the single spin time is 10min, then
Solid is collected with the dry 10h of 70 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4.After regulation
g-C3N4Performance parameter is as shown in figure 4d.
Embodiment 5
1) by 400mg g-C to be regulated and controled3N4With 200mg NaBH4It is sufficiently mixed 20min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 150mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 20 DEG C/s
500 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 12000r/min, the single spin time is 10min, then
Solid is collected with the dry 10h of 80 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4.After regulation
g-C3N4Performance parameter is as fig 5d.
Embodiment 6
1) by 400mg g-C to be regulated and controled3N4With 300mg NaBH4It is sufficiently mixed 25min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 200mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 20 DEG C/s
550 DEG C of calcination temperature is risen to from room temperature, then calcines 0.5h at calcination temperatures, and then cooled to room temperature obtains mixture
B;
3) by mixture B centrifugation washing 4 times, centrifugal rotational speed 12000r/min, the single spin time is 5min, is then received
Collect solid with the dry 8h of 80 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4。
Embodiment 7
1) by 400mg g-C to be regulated and controled3N4With 400mg NaBH4It is sufficiently mixed 30min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 250mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 25 DEG C/s
550 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 12000r/min, the single spin time is 5min, is then received
Collect solid with the dry 6h of 80 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4。
Embodiment 8
1) by 400mg g-C to be regulated and controled3N4With 80mg NaBH4It is sufficiently mixed 5min, obtains uniform g-C3N4-NaBH4It is mixed
Close object A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 250mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 30 DEG C/s
600 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 15000r/min, the single spin time is 5min, is then received
Collect solid with the dry 6h of 80 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4。
Embodiment 9
1) by 400mg g-C to be regulated and controled3N4With 350mg NaBH4It is sufficiently mixed 30min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 250mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 25 DEG C/s
580 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 13000r/min, the single spin time is 5min, is then received
Collect solid with the dry 6h of 90 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4。
Embodiment 10
1) by 400mg g-C to be regulated and controled3N4With 250mg NaBH4It is sufficiently mixed 20min, obtains uniform g-C3N4-NaBH4
Mixture A;
2) crucible equipped with mixture A is put into and is rapidly heated in tube furnace, used nitrogen as protection gas in tube furnace, forge
Protection gas 3 times, air velocity 250mL/min are vacuumized-led to before burning repeatedly;Tube furnace is when calcining with the heating rate of 10 DEG C/s
300 DEG C of calcination temperature is risen to from room temperature, then calcines 1h at calcination temperatures, and then cooled to room temperature obtains mixture B;
3) by mixture B centrifugation washing 3 times, centrifugal rotational speed 14000r/min, the single spin time is 5min, is then received
Collect solid with the dry 6h of 70 DEG C of temperature in vacuum drying oven, obtaining target product is the g-C after regulating and controlling3N4。
The present invention passes through will g-C be regulated and controled3N4With NaBH4According to mass ratio (1~5): 1 be uniformly mixed obtain mixture A,
Then 0.5~2h is calcined at 300~600 DEG C, makes NaBH at 300~600 DEG C4In thermal decomposition temperature, decomposes and generate work
Property B3+With active H-, wherein B3+By replacing g-C3N4In C and enter g-C3N4, i.e. introducing B doping;H-It is gone back with high
Originality makes g-C3N4In part N with NH3Form missing, i.e., introducing N defect, using B doping and N defect can reduce g-C3N4
Conduction band and valence band location, to reduce g-C3N4Forbidden bandwidth, while B doping and the introducing of N defect can mutually promote,
Reach a very high introducing density, causes g-C3N4The substantially change of electronic structure, thus substantially modulation g-C3N4Energy band knot
Structure, the method for the present invention is simple, wide to the band engineering range of graphite phase carbon nitride, and controllability is strong, reproducible, raw material it is cheap and
From a wealth of sources, green safe environmental protection improves production efficiency, reduces production cost, is suitble to large-scale production.The present invention utilizes
The easily operated method of safety realizes g-C3N4The substantially modulation of forbidden bandwidth, conduction band and valence band location.The g- that band engineering is crossed
C3N4Good dispersion, it is storage-stable.Organic solvent-free and heavy metal chemical reagent participate in this method during the reaction, not only
Problem of environmental pollution can be effectively avoided, simultaneously because the g-C that band engineering is crossed3N4Nontoxic characteristic can be widely used in light
The fields such as water, artificial photosynthesis, organic pollutant degradation and gas oxidation/reduction are catalytically decomposed.Entire preparation of the invention
Process is easy to operate.
G-C after the regulation obtained according to embodiment 1 to embodiment 53N4Performance parameter, by Fig. 1-to Fig. 5 band structure figure
As can be seen that the g-C after regulating and controlling by the method for the invention3N4Forbidden bandwidth and position of energy band obtained ideal substantially modulation,
It is 2.66~1.40eV by the forbidden bandwidth range of graphite phase carbon nitride that the present invention obtains, conduction band potential range is -0.95~
1.10V vs standard hydrogen electrode, valence band potential range is 1.71~2.50V vs standard hydrogen electrode, relative to the g-C before adjustment3N4
Have and significantly changes.
It should be pointed out that described above and preferred embodiment may not be interpreted as limiting design philosophy of the invention.Ability
Technical thought of the invention can be improved in the form of various and be changed by field technique personnel, and such improvement and change should be understood that
In belonging to the scope of protection of the present invention.
Claims (8)
1. a kind of graphite phase carbon nitride band engineering method, which comprises the following steps:
Step 1), will g-C be regulated and controled3N4With NaBH4According to mass ratio (1~5): 1 be uniformly mixed obtain mixture A;
Step 2) carries out mixture A to calcine the band engineering that graphite phase carbon nitride can be completed under atmosphere of inert gases, forges
Burning temperature is 300~600 DEG C, and calcination time is 0.5~2h.
2. a kind of graphite phase carbon nitride band engineering method according to claim 1, which is characterized in that mixture A exists
Mixture B is obtained after being calcined under atmosphere of inert gases, and mixture B is placed on vacuum drying oven drying by being centrifuged washing,
Graphite phase carbon nitride after band engineering can be obtained after drying.
3. a kind of graphite phase carbon nitride band engineering method according to claim 2, which is characterized in that according to the above method
The forbidden bandwidth range of obtained graphite phase carbon nitride is 2.66~1.40eV, and conduction band potential range is -0.95~1.10V vs
Standard hydrogen electrode, valence band potential range are 1.71~2.50V vs standard hydrogen electrode.
4. a kind of graphite phase carbon nitride band engineering method according to claim 2, which is characterized in that centrifugation washing 3~6
Secondary, centrifugal rotational speed is 6000~15000r/min, and centrifugation time is 5~15min.
5. a kind of graphite phase carbon nitride band engineering method according to claim 1, which is characterized in that by g-C3N4With
NaBH4According to mass ratio (1~5): 1 is placed in mortar, and being stirred 5~30min by grinding can be obtained uniform mixing
Object A.
6. a kind of graphite phase carbon nitride band engineering method according to claim 1, which is characterized in that, will in step 2)
Mixture A is put into togerther in tube furnace after being put into crucible, and inert gas is passed through into tube furnace as protective gas, by tube furnace
300~600 DEG C of calcination temperature is risen to from room temperature with the heating rate of 10~30 DEG C/s, then in 300~600 DEG C of calcination temperature
0.5~2h of lower calcining, then the band engineering of graphite phase carbon nitride can be completed in cooled to room temperature.
7. a kind of graphite phase carbon nitride band engineering method according to claim 6, which is characterized in that put mixture A
Enter to be put into togerther after tube furnace after crucible and tube furnace is vacuumized repeatedly-led to protection gas 3~5 times.
8. a kind of graphite phase carbon nitride band engineering method according to claim 1 or 6, which is characterized in that inert gas
Using nitrogen or argon gas.
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CN111215118A (en) * | 2020-02-18 | 2020-06-02 | 盐城工学院 | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof |
CN111410178A (en) * | 2020-04-22 | 2020-07-14 | 内蒙古民族大学 | Graphitized boron carbon nitrogen material and preparation method and application thereof |
CN113477269A (en) * | 2021-07-02 | 2021-10-08 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
CN114214663A (en) * | 2022-01-06 | 2022-03-22 | 武汉工程大学 | Nitrogen vacancy modified nickel nitride electrocatalytic material and preparation method and application thereof |
CN115025804A (en) * | 2022-06-30 | 2022-09-09 | 哈尔滨工程大学 | Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof |
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CN107744824A (en) * | 2017-04-19 | 2018-03-02 | 华中科技大学 | A kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application |
CN108355701A (en) * | 2018-03-23 | 2018-08-03 | 辽宁大学 | Ag supports two-dimentional graphite phase carbon nitride nanosheet photocatalyst and its preparation method and application |
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CN105233850A (en) * | 2015-09-21 | 2016-01-13 | 河海大学 | Magnetic nanometer composite photocatalysis material, and preparation method thereof |
CN107744824A (en) * | 2017-04-19 | 2018-03-02 | 华中科技大学 | A kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application |
CN108355701A (en) * | 2018-03-23 | 2018-08-03 | 辽宁大学 | Ag supports two-dimentional graphite phase carbon nitride nanosheet photocatalyst and its preparation method and application |
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CN111215118A (en) * | 2020-02-18 | 2020-06-02 | 盐城工学院 | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof |
CN111215118B (en) * | 2020-02-18 | 2022-08-23 | 盐城工学院 | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof |
CN111410178A (en) * | 2020-04-22 | 2020-07-14 | 内蒙古民族大学 | Graphitized boron carbon nitrogen material and preparation method and application thereof |
CN113477269A (en) * | 2021-07-02 | 2021-10-08 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
CN113477269B (en) * | 2021-07-02 | 2023-03-14 | 中国科学技术大学 | Continuous regulation and control method of carbon nitride energy band structure and method for preparing hydrogen peroxide through photocatalysis |
CN114214663A (en) * | 2022-01-06 | 2022-03-22 | 武汉工程大学 | Nitrogen vacancy modified nickel nitride electrocatalytic material and preparation method and application thereof |
CN115025804A (en) * | 2022-06-30 | 2022-09-09 | 哈尔滨工程大学 | Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof |
CN115025804B (en) * | 2022-06-30 | 2023-01-31 | 哈尔滨工程大学 | Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof |
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