CN107570190A - The preparation method of carbon doping carbon nitride films electrode - Google Patents
The preparation method of carbon doping carbon nitride films electrode Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of carbon doping carbon nitride films electrode, comprise the following steps：S1, by raw material of melamine, cyanuric acid and barbiturates prepare carbon doping carbonitride；S2, carbon doping obtained by step S1 nitrogenized into carbon dissolution, coated on pretreated tin dioxide transparent conductive glass, after baking carbon doping carbon nitride films electrode.The present invention has the advantages that technique is simple, cost is cheap.
Description
Technical field
The present invention relates to non-metal semiconductive carbon nitride material field, more particularly to a kind of carbon doping carbon nitride films electrode
Preparation method.
Background technology
With the gradual shortage of fossil energy, increasing people is transferred to sight in the regenerative resources such as solar energy.
Photocatalitic Technique of Semiconductor causes the extensive concern of researcher, while can also solve the problems of energy and environment.Light
Catalytic process mainly includes following 3 stages：（1）The capture of light,（2）The separation and transport of photo-generated carrier,（3）Reactant exists
Reacted at interface.But photo-generated carrier easily occur it is compound.In order to avoid such unfavorable factor, further improve too
The conversion efficiency of positive energy, it is necessary to design the photochemical catalyst of high separating efficiency.Photoelectric material may be used as luminaire, and optics is visited
Device, photoelectrochemical cell etc. is surveyed, and these applications need to prepare electrode film.
Recently, metal-free graphite phase carbon nitride semiconductive thin film separates in water, degradation of organic substances and sensor skill
Art has larger application.The unique semiconductor energy band structure of carbonitride allows it to make full use of visible ray be catalyzed instead
Should.Carbon nitride films electrode prepared by conventional method still suffers from electronics and hole separation is incomplete, electronics because specific surface area is small
Transmission speed is slow, and the shortcomings of again compound occurs.At present, by graphite phase carbon nitride the methods of generally use drop coating, dip-coating
Powder is prepared in electrode material surface, and the graphite phase carbon nitride powder of the electrode surface of acquisition is uneven, and is easy to come off, and causes
Electrode is unstable.
The content of the invention
The technical problems to be solved by the invention are in view of the shortcomings of the prior art, there is provided a kind of technique is simple, cost is low
The preparation method of honest and clean carbon doping carbon nitride films electrode.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of preparation method of carbon doping carbon nitride films electrode, comprises the following steps：
S1, by raw material of melamine, cyanuric acid and barbiturates prepare carbon doping carbonitride；
S2, carbon doping obtained by step S1 nitrogenized into carbon dissolution, coated on pretreated tin dioxide transparent conductive glass, dried
Carbon doping carbon nitride films electrode is obtained after roasting.
As the further improvement to above-mentioned technical proposal：
The step S1 is specially：
S1-1, by melamine, cyanuric acid and barbiturates grind, be dissolved in solvent I, stir, dry after presoma；
S1-2, presoma obtained by step S1-2 calcined, after grinding carbon doping carbonitride.
The mass ratio of melamine, cyanuric acid and barbiturates is 1: 1: 0.1~0.2 in the step S1-1；It is described
Solvent I is water.
In the step S1-2, the calcination process is specially：400~550 are heated to 2~4 DEG C/min speed
DEG C, calcine 3~6h.
The step S2 is specially：
S2-1, carbon doping carbonitride obtained by step S1 is dissolved in solvent II, after ultrasound solution electrode；
S2-2, step S2-1 the electrode obtained solution is spun on pretreated tin dioxide transparent conductive glass, obtains wet film；
S2-3, carbon doping carbon nitride films electrode will be obtained after wet film baking obtained by step S2-2.
In the step S2-1, the solvent II is the one or more in ethanol, polyvinyl alcohol and perfluorinated sulfonic acid；It is described
The frequency of ultrasound is 5~10KHz, and the ultrasonic time is 3~5min.
In the step S2-2, the preprocessing process is specially：By tin dioxide transparent conductive glass successively with water, second
Alcohol, acetone respectively clean 2~3 times.
In the step S2-2, the rotating speed of the spin coating is 3800~4000r/min, and the time of spin coating is 40~60s.
The step S2-3 is specially：10min is toasted at a temperature of wet film is placed in into 140~150 DEG C, obtains carbon doping nitridation
C film electrode.
The preparation method also includes repeat step S2-2 and step S2-3, until the thickness of carbon doping carbon nitride films electrode
Degree reaches preset value.
Compared with prior art, the advantage of the invention is that：
A kind of preparation method of carbon doping carbon nitride films electrode of the present invention, prepares carbon doping using the method for ternary polymerization first
Carbonitride, carbon doping carbonitride is then obtained into carbon doping carbon nitride films electrode coated on tin dioxide transparent conductive glass,
Technique is simple, and cost is cheap, and the energy band that obtained carbon doping carbon nitride films electrode changes carbonitride by inorganic elements C is tied
Structure, the specific surface area of carbonitride is greatly improved, makes electronics and hole separation more efficient, improve photo-signal, reduce resistance,
Sensitivity is improved, there are good photoelectric properties, meet actual production demand, had broad application prospects in photocatalysis field.
Brief description of the drawings
Fig. 1 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride XRD.
Fig. 2 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride TEM figure.
Fig. 3 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride DRS figure.
Fig. 4 is the density of photocurrent that carbon doping carbon nitride films electrode in carbon electrode and embodiment 1 is nitrogenized in comparative example 1
Figure.
Fig. 5 is the impedance diagram that carbon doping carbon nitride films electrode in carbon electrode and embodiment 1 is nitrogenized in comparative example 1.
Embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Raw material and instrument employed in following examples are commercially available.
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and with 300W xenon lamps（Middle religion Jin Yuan) it is used as visible ray
Source.The ultraviolet light of xenon lamp is filtered with 420nm optical filters.Electrochemistry experiment uses CHI660B electrochemical workstation (Shanghai Chen Huas
Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is working electrode, and platinum electrode is sweet to electrode, saturation
Mercury electrode (SCE) is reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment is in room temperature 0.2mol/L sodium sulphate
Carried out in solution (pH=7.0), current potential is -0.2V (vs SCE).EIS experiments are entered in containing 0.2mol/L metabisulfite solutions
OK, frequency range is 0.01Hz~100kHz, initial potential 0.24V, AC amplitude 5mV.
Embodiment 1：The preparation of carbon doping carbon nitride films electrode
A kind of preparation method of carbon doping carbon nitride films electrode, comprises the following steps：
S1, by raw material of melamine, cyanuric acid and barbiturates prepare carbon doping carbonitride；
S1-1, take 10g melamines, 10g cyanuric acids, 1g barbiturates, grinding, be dissolved in 100ml water, using rotating speed as
300r/min ball milling 0.5h, 2h is stirred, is dried on electrothermal furnace, presoma is made.
S1-2, presoma is placed in Muffle furnace, 550 DEG C are heated to 2.5 DEG C/min heating rate, and in 550 DEG C of guarantors
Warm 4h, takes out block after natural cooling, grinds 20 minutes, is respectively rinsed 3 times with water and ethanol, filtering, is dried at 80 DEG C
12h, produce porous carbon doping carbonitride.
S2, carbon doping obtained by step S1 nitrogenized into carbon dissolution, coated on pretreated tin dioxide transparent conductive glass
On, carbon doping carbon nitride films electrode is obtained after baking.
By tin dioxide transparent conductive glass（FTO）Respectively cleaned 2 times with deionized water, ethanol, acetone successively, by carbon doping
Carbonitride is dissolved to ethanol（Identical technique effect is also can reach using polyvinyl alcohol, perfluorinated sulfonic acid）In, with 10kHz frequency
Ultrasonic 5min, obtains solution electrode, and solution electrode is revolved on Tu 40s to FTO with 4000r/min rotating speed, obtains wet film.
Wet film is placed in 150 DEG C of warm table and toasts 10min.
Repeat rotation Tu baking procedure 8 times, obtain carbon doping carbon nitride films electrode.
A kind of preparation method of carbon doping carbon nitride films electrode of the present invention, prepares carbon using the method for ternary polymerization first
Carbonitride is adulterated, carbon doping carbonitride is then obtained into carbon doping carbon nitride films coated on tin dioxide transparent conductive glass
Electrode, technique is simple, and cost is cheap, and obtained carbon doping carbon nitride films electrode changes carbonitride by inorganic elements C
Band structure, the specific surface area of carbonitride is greatly improved, electronics and hole is separated more efficient, raising photo-signal, drop
Low resistance, sensitivity is improved, there are good photoelectric properties, meet actual production demand, there is wide answer in photocatalysis field
Use prospect.
Comparative example 1：The preparation of the nitridation carbon electrode of carbon doping is not carried out
Take 10g melamines to be put into crucible, be placed in Muffle furnace, 550 DEG C are heated to 2.5 DEG C/min heating rate, and
4h is incubated at 550 DEG C, takes out block after natural cooling, is ground 20 minutes, is respectively rinsed 3 times with water and ethanol, filtering, 80 DEG C
Lower dry 12h, produces carbonitride.
By tin dioxide transparent conductive glass（FTO）Cleaned 2 times with water, ethanol, acetone successively, carbonitride ethanol is molten
Solution, with 10kHz frequency ultrasound 5min, obtains solution electrode.Solution electrode is revolved on Tu 40s to FTO with 4000r/min rotating speed,
Wet film is obtained, wet film is placed in 150 DEG C of warm table and toasts 10min, carbon electrode must be nitrogenized 8 times by repeating to revolve Tu baking procedure.
Performance test：Fig. 1 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride XRD, can from figure
Significantly graphite phase carbon nitride is belonged to find that the carbonitride of comparative example 1 occurs two at 13.0 ° and 27.5 °（100）With
（002）The XRD diffraction maximums of crystal face, it was demonstrated that the product of preparation is carbonitride.Relative to comparative example 1, modified carbon in embodiment 1
27.5 ° of peak intensities of doping carbonitride die down, and illustrate that the thickness of carbon doping carbonitride is thinning, more conducively electronics and hole separation.
Fig. 2 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride TEM figure, from figure（a）In it can be seen that
The carbonitride of comparative example 1 is smooth, and schemes（b）There is nano aperture not of uniform size in the carbon doping carbonitride of embodiment 1, shows
Obvious nanometer laminated structure, relative to traditional reunion shape carbonitride（g-C3N4）Specific surface area is bigger, illustrates that carbon doping nitrogenizes
Carbon can promote effective transmission of electronics, suppress the compound again of electronics and hole.
Fig. 3 be comparative example 1 carbonitride and embodiment 1 carbon doping carbonitride DRS figure, as can be seen from the figure contrast
The maximum absorption wavelength of the carbonitride of example 1 in 475nm or so, carbon doping carbonitride prepared by embodiment 1 by wavelength widen to
More than 650nm, the absorption region of light is added, improve the utilization rate of light.
Fig. 4 is the density of photocurrent that carbon doping carbon nitride films electrode in carbon electrode and embodiment 1 is nitrogenized in comparative example 1
Figure.Compared with nitrogenizing carbon electrode in comparative example 1, the density of photocurrent enhancing 2 of carbon doping carbon nitride films electrode in embodiment 1
Times.
Fig. 5 is the impedance diagram that carbon doping carbon nitride films electrode in carbon electrode and embodiment 1 is nitrogenized in comparative example 1.With it is right
Nitrogenize carbon electrode in ratio 1 to compare, the impedance reduction of carbon doping carbon nitride films electrode in embodiment 1.Impedance reflects resistance
Power, under certain voltage, resistance is smaller, and electric current is bigger, and Fig. 4 and Fig. 5 conclusion are mutually supported.
Although the present invention is disclosed above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with ability
The technical staff in domain, in the case where not departing from technical solution of the present invention scope, all using the technology contents pair of the disclosure above
Technical solution of the present invention makes many possible changes and modifications, or is revised as the equivalent embodiment of equivalent variations.Therefore, it is every
Without departing from the content of technical solution of the present invention, according to the technology of the present invention essence to any simple modification made for any of the above embodiments,
Equivalent variations and modification, it all should fall in the range of technical solution of the present invention protection.
Claims (10)
1. a kind of preparation method of carbon doping carbon nitride films electrode, it is characterised in that comprise the following steps：
S1, by raw material of melamine, cyanuric acid and barbiturates prepare carbon doping carbonitride；
S2, carbon doping obtained by step S1 nitrogenized into carbon dissolution, coated on pretreated tin dioxide transparent conductive glass, dried
Carbon doping carbon nitride films electrode is obtained after roasting.
2. preparation method according to claim 1, it is characterised in that the step S1 is specially：
S1-1, by melamine, cyanuric acid and barbiturates grind, be dissolved in solvent I, stir, dry after presoma；
S1-2, presoma obtained by step S1-2 calcined, after grinding carbon doping carbonitride.
3. preparation method according to claim 2, it is characterised in that melamine, cyanuric acid in the step S1-1
Mass ratio with barbiturates is 1: 1: 0.1~0.2；The solvent I is water.
4. preparation method according to claim 2, it is characterised in that in the step S1-2, the calcination process is specific
For：400~550 DEG C are heated to 2~4 DEG C/min speed, calcines 3~6h.
5. preparation method according to any one of claim 1 to 4, it is characterised in that the step S2 is specially：
S2-1, carbon doping carbonitride obtained by step S1 is dissolved in solvent II, after ultrasound solution electrode；
S2-2, step S2-1 the electrode obtained solution is spun on pretreated tin dioxide transparent conductive glass, obtains wet film；
S2-3, carbon doping carbon nitride films electrode will be obtained after wet film baking obtained by step S2-2.
6. preparation method according to claim 5, it is characterised in that in the step S2-1, the solvent II be ethanol,
One or more in polyvinyl alcohol and perfluorinated sulfonic acid；The ultrasonic frequency is 5~10kHz, the ultrasonic time is 3~
5min。
7. preparation method according to claim 5, it is characterised in that in the step S2-2, the preprocessing process tool
Body is：Tin dioxide transparent conductive glass is respectively cleaned 2~3 times with water, ethanol, acetone successively.
8. preparation method according to claim 5, it is characterised in that in the step S2-2, the rotating speed of the spin coating is
3800~4000r/min, the time of spin coating is 40~60s.
9. preparation method according to claim 5, it is characterised in that the step S2-3 is specially：Wet film is placed in 140
10min is toasted at a temperature of~150 DEG C, obtains carbon doping carbon nitride films electrode.
10. preparation method according to claim 5, it is characterised in that the preparation method also includes repeat step S2-2
With step S2-3, until the thickness of carbon doping carbon nitride films electrode reaches preset value.
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Cited By (7)
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| CN108906111A (en) * | 2018-07-26 | 2018-11-30 | 湖南大学 | Self assembly is copolymerized carbonitride optic catalytic composite material and its preparation method and application |
| CN109529904A (en) * | 2018-12-19 | 2019-03-29 | 江苏大学 | A kind of preparation method of the carbon nitride photocatalyst of surface amorphous carbon doping |
| CN111167501A (en) * | 2020-02-06 | 2020-05-19 | 北京工商大学 | Visible light response photocatalytic material, preparation thereof and application thereof in micro-polluted water treatment |
| CN112456612A (en) * | 2020-11-13 | 2021-03-09 | 西安建筑科技大学 | Copper-doped carbon nitride electrode, preparation method and application thereof |
| CN114225957A (en) * | 2021-12-31 | 2022-03-25 | 西南大学 | Carbon-doped supermolecule polymeric carbon nitride visible-light-induced photocatalyst and application thereof |
| CN114591733A (en) * | 2020-12-03 | 2022-06-07 | 南京大学 | Preparation method of graphite-phase carbon nitride fluorescent powder with controllable fluorescence emission wavelength |
| CN115385420A (en) * | 2022-07-29 | 2022-11-25 | 江苏理工学院 | In-situ controllable preparation method and application of phosphorus-doped carbon nitride electrode |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906111A (en) * | 2018-07-26 | 2018-11-30 | 湖南大学 | Self assembly is copolymerized carbonitride optic catalytic composite material and its preparation method and application |
| CN109529904A (en) * | 2018-12-19 | 2019-03-29 | 江苏大学 | A kind of preparation method of the carbon nitride photocatalyst of surface amorphous carbon doping |
| CN111167501A (en) * | 2020-02-06 | 2020-05-19 | 北京工商大学 | Visible light response photocatalytic material, preparation thereof and application thereof in micro-polluted water treatment |
| CN111167501B (en) * | 2020-02-06 | 2022-12-06 | 北京工商大学 | Visible light response photocatalytic material, preparation thereof and application thereof in micro-polluted water treatment |
| CN112456612A (en) * | 2020-11-13 | 2021-03-09 | 西安建筑科技大学 | Copper-doped carbon nitride electrode, preparation method and application thereof |
| CN114591733A (en) * | 2020-12-03 | 2022-06-07 | 南京大学 | Preparation method of graphite-phase carbon nitride fluorescent powder with controllable fluorescence emission wavelength |
| CN114225957A (en) * | 2021-12-31 | 2022-03-25 | 西南大学 | Carbon-doped supermolecule polymeric carbon nitride visible-light-induced photocatalyst and application thereof |
| CN115385420A (en) * | 2022-07-29 | 2022-11-25 | 江苏理工学院 | In-situ controllable preparation method and application of phosphorus-doped carbon nitride electrode |
| CN115385420B (en) * | 2022-07-29 | 2023-11-03 | 江苏理工学院 | In-situ controllable preparation method and application of phosphorus-doped carbon nitride electrode |
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