CN107570190B - Preparation method of carbon-doped carbon nitride film electrode - Google Patents
Preparation method of carbon-doped carbon nitride film electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon-doped carbon nitride film electrode, which comprises the following steps: s1, preparing carbon-doped carbon nitride by taking melamine, cyanuric acid and barbituric acid as raw materials; and S2, dissolving the carbon-doped carbon nitride obtained in the step S1, coating the solution on the pretreated tin dioxide transparent conductive glass, and baking to obtain the carbon-doped carbon nitride film electrode. The invention has the advantages of simple process, low cost and the like.
Description
Technical Field
The invention relates to the field of non-metal semiconductor carbon nitride materials, in particular to a preparation method of a carbon-doped carbon nitride film electrode.
Background
With the gradual shortage of fossil energy, more and more people are looking to renewable energy sources such as solar energy. Semiconductor photocatalysis technology has attracted extensive attention of researchers, and can solve a plurality of problems of energy and environment. The photocatalytic process mainly comprises the following 3 stages: (1) light capture, (2) separation and transport of photogenerated carriers, and (3) reaction of reactants at an interface. However, photogenerated carriers are susceptible to recombination. In order to avoid such a disadvantage and to further improve the conversion efficiency of solar energy, it is necessary to design a photocatalyst having a high separation efficiency. The photoelectric material can be used in the aspects of light-emitting equipment, optical detector, photoelectrochemical cell and the like, and the application needs to prepare an electrode film.
Recently, the graphite phase carbon nitride semiconductor film without metal has a great application in water separation, organic matter degradation and sensor technology. The unique semiconductor band structure of carbon nitride makes it possible to utilize visible light to catalyze reactions. The carbon nitride film electrode prepared by the traditional method still has the defects of incomplete separation of electrons and holes, low electron transmission speed, recombination and the like due to small specific surface area. At present, graphite phase carbon nitride powder is prepared on the surface of an electrode material by methods such as drop coating, dip coating and the like, and the obtained graphite phase carbon nitride powder on the surface of the electrode is not uniform and is easy to fall off, so that the electrode is unstable.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a carbon-doped carbon nitride film electrode, which has simple process and low cost and aims at overcoming the defects of the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a carbon-doped carbon nitride film electrode comprises the following steps:
s1, preparing carbon-doped carbon nitride by taking melamine, cyanuric acid and barbituric acid as raw materials;
and S2, dissolving the carbon-doped carbon nitride obtained in the step S1, coating the solution on the pretreated tin dioxide transparent conductive glass, and baking to obtain the carbon-doped carbon nitride film electrode.
As a further improvement to the above technical solution:
the step S1 specifically includes:
s1-1, grinding melamine, cyanuric acid and barbituric acid, dissolving in a solvent I, stirring, and drying to obtain a precursor;
s1-2, calcining the precursor obtained in the step S1-2, and grinding to obtain the carbon-doped carbon nitride.
The mass ratio of the melamine to the cyanuric acid to the barbituric acid in the step S1-1 is 1: 0.1-0.2; the solvent I is water.
In the step S1-2, the calcination process specifically includes: heating to 400-550 ℃ at the speed of 2-4 ℃/min, and calcining for 3-6 h.
The step S2 specifically includes:
s2-1, dissolving the carbon-doped carbon nitride obtained in the step S1 in a solvent II, and performing ultrasonic treatment to obtain an electrode solution;
s2-2, spin-coating the electrode solution obtained in the step S2-1 on pretreated tin dioxide transparent conductive glass to obtain a wet film;
s2-3, baking the wet film obtained in the step S2-2 to obtain the carbon-doped carbon nitride film electrode.
In the step S2-1, the solvent ii is one or more of ethanol, polyvinyl alcohol and perfluorosulfonic acid; the frequency of the ultrasonic wave is 5-10 KHz, and the time of the ultrasonic wave is 3-5 min.
In the step S2-2, the preprocessing process specifically includes: and (3) sequentially washing the tin dioxide transparent conductive glass with water, ethanol and acetone for 2-3 times respectively.
In the step S2-2, the rotation speed of the spin coating is 3800-4000 r/min, and the spin coating time is 40-60S.
The step S2-3 specifically includes: and (3) baking the wet film at the temperature of 140-150 ℃ for 10min to obtain the carbon-doped carbon nitride film electrode.
The preparation method further comprises the step of repeating the step S2-2 and the step S2-3 until the thickness of the carbon-doped carbon nitride film electrode reaches a preset value.
Compared with the prior art, the invention has the advantages that:
the invention relates to a preparation method of a carbon-doped carbon nitride film electrode, which comprises the steps of firstly preparing carbon-doped carbon nitride by adopting a ternary polymerization method, and then coating the carbon-doped carbon nitride on tin dioxide transparent conductive glass to obtain the carbon-doped carbon nitride film electrode.
Drawings
Figure 1 is an XRD pattern of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1.
Fig. 2 is a TEM image of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1.
Figure 3 is a DRS plot of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1.
Fig. 4 is a graph of photocurrent density for the carbon nitride electrode of comparative example 1 and the carbon-doped carbon nitride thin film electrode of example 1.
Fig. 5 is a graph showing the impedance of the carbon nitride electrode of comparative example 1 and the carbon-doped carbon nitride thin film electrode of example 1.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples.
The starting materials and equipment used in the following examples are commercially available.
The light source is taken from a high-brightness xenon lamp parallel light source system instrument, and a 300W xenon lamp (a middle school gold source) is taken as a visible light source. The UV light from the xenon lamp was filtered off with a 420nm filter. Electrochemical experiments used the CHI660B electrochemical workstation (shanghai chenhua instruments ltd) with a conventional three-electrode system: the modified electrode was the working electrode, the platinum wire electrode was the counter electrode, and the Saturated Calomel Electrode (SCE) was the reference electrode (all potentials were relative to SCE). Electrochemical experiments were all performed at room temperature in 0.2mol/L sodium sulfate solution (pH =7.0) at a potential of-0.2 v (vs sce). EIS experiments were carried out in a solution containing 0.2mol/L sodium sulfate, with a frequency ranging from 0.01Hz to 100kHz, an initial potential of 0.24V and an AC amplitude of 5 mV.
Example 1: preparation of carbon-doped carbon nitride film electrode
A preparation method of a carbon-doped carbon nitride film electrode comprises the following steps:
s1, preparing carbon-doped carbon nitride by taking melamine, cyanuric acid and barbituric acid as raw materials;
s1-1, taking 10g of melamine, 10g of cyanuric acid and 1g of barbituric acid, grinding, dissolving in 100ml of water, ball-milling for 0.5h at the rotating speed of 300r/min, stirring for 2h, and drying on an electric heating furnace to obtain the precursor.
And S1-2, placing the precursor in a muffle furnace, heating to 550 ℃ at the heating rate of 2.5 ℃/min, preserving heat for 4h at 550 ℃, taking out the block after natural cooling, grinding for 20 min, washing 3 times with water and ethanol respectively, filtering, and drying for 12h at 80 ℃ to obtain the porous carbon-doped carbon nitride.
And S2, dissolving the carbon-doped carbon nitride obtained in the step S1, coating the solution on the pretreated tin dioxide transparent conductive glass, and baking to obtain the carbon-doped carbon nitride film electrode.
Sequentially washing tin dioxide transparent conductive glass (FTO) with deionized water, ethanol and acetone for 2 times respectively, dissolving carbon-doped carbon nitride into ethanol (the same technical effect can be achieved by using polyvinyl alcohol and perfluorosulfonic acid), carrying out ultrasonic treatment for 5min at the frequency of 10kHz to obtain an electrode solution, and coating the electrode solution on the FTO at the rotating speed of 4000r/min for 40s to obtain the wet film.
The wet film was baked for 10min on a heating stage at 150 ℃.
And repeating the spin coating and baking step for 8 times to obtain the carbon-doped carbon nitride film electrode.
The invention relates to a preparation method of a carbon-doped carbon nitride film electrode, which comprises the steps of firstly preparing carbon-doped carbon nitride by adopting a ternary polymerization method, and then coating the carbon-doped carbon nitride on tin dioxide transparent conductive glass to obtain the carbon-doped carbon nitride film electrode.
Comparative example 1: preparation of carbon nitride electrode without carbon doping
And (2) putting 10g of melamine into a crucible, putting the crucible into a muffle furnace, heating the crucible to 550 ℃ at the heating rate of 2.5 ℃/min, preserving the heat at 550 ℃ for 4h, taking out the block after natural cooling, grinding the block for 20 min, washing the block for 3 times by using water and ethanol respectively, filtering the block, and drying the block at 80 ℃ for 12h to obtain the carbon nitride.
Cleaning tin dioxide transparent conductive glass (FTO) with water, ethanol and acetone sequentially for 2 times, dissolving carbon nitride with ethanol, and performing ultrasonic treatment at 10kHz frequency for 5min to obtain electrode solution. And (3) spinning the electrode solution on FTO for 40s at the rotating speed of 4000r/min to obtain a wet film, baking the wet film on a heating table at 150 ℃ for 10min, and repeating the spinning and baking step for 8 times to obtain the carbon nitride electrode.
And (3) performance testing: fig. 1 is an XRD pattern of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1, from which it can be found that the carbon nitride of comparative example 1 has two distinct XRD diffraction peaks ascribed to (100) and (002) crystal planes of graphite-phase carbon nitride at 13.0 ° and 27.5 °, confirming that the prepared product is carbon nitride. The reduced 27.5 peak intensity of the modified carbon-doped carbon nitride in example 1 relative to comparative example 1 indicates that the carbon-doped carbon nitride is thinner, more favorable for electron and hole separation.
FIG. 2 is a TEM image of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1, wherein it can be seen from the image (a) that the carbon nitride of comparative example 1 is smooth, while the image (b) the carbon-doped carbon nitride of example 1 shows nano-pores with different sizes, and shows a distinct nano-layered structure, compared to the conventional agglomerated carbon nitride (g-C)3N4) The larger specific surface area indicates that the carbon is doped with carbon nitrideEffective transfer of electrons can be promoted, and recombination of electrons and holes can be suppressed.
Fig. 3 is a DRS diagram of the carbon nitride of comparative example 1 and the carbon-doped carbon nitride of example 1, and it can be seen from the DRS diagram that the maximum absorption wavelength of the carbon nitride of comparative example 1 is about 475nm, and the carbon-doped carbon nitride prepared in example 1 widens the wavelength to over 650nm, which increases the absorption range of light and improves the utilization rate of light.
Fig. 4 is a graph of photocurrent density for the carbon nitride electrode of comparative example 1 and the carbon-doped carbon nitride thin film electrode of example 1. The photocurrent density of the carbon-doped carbon nitride thin film electrode in example 1 was increased by 2 times compared to the carbon nitride electrode in comparative example 1.
Fig. 5 is a graph showing the impedance of the carbon nitride electrode of comparative example 1 and the carbon-doped carbon nitride thin film electrode of example 1. The resistance of the carbon-doped carbon nitride thin film electrode in example 1 was reduced compared to the carbon nitride electrode in comparative example 1. The impedance reflects the strength of the resistance, and at a certain voltage, the smaller the resistance, the larger the current, and the conclusions of fig. 4 and fig. 5 are mutually supported.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments to equivalent variations, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (7)
1. A preparation method of a carbon-doped carbon nitride film electrode is characterized by comprising the following steps:
s1, preparing carbon-doped carbon nitride by taking melamine, cyanuric acid and barbituric acid as raw materials;
s2, dissolving the carbon-doped carbon nitride obtained in the step S1, coating the dissolved carbon-doped carbon nitride on pretreated tin dioxide transparent conductive glass, and baking the tin dioxide transparent conductive glass at the temperature of 140-150 ℃ to obtain a carbon-doped carbon nitride film electrode;
the step S1 specifically includes:
s1-1, grinding melamine, cyanuric acid and barbituric acid, dissolving in a solvent I, stirring, and drying to obtain a precursor;
s1-2, calcining the precursor obtained in the step S1-1, and grinding to obtain carbon-doped carbon nitride;
the mass ratio of the melamine to the cyanuric acid to the barbituric acid is 1: 0.1-0.2;
the step S2 specifically includes:
s2-1, dissolving the carbon-doped carbon nitride obtained in the step S1 in a solvent II, and performing ultrasonic treatment to obtain an electrode solution;
s2-2, spin-coating the electrode solution obtained in the step S2-1 on pretreated tin dioxide transparent conductive glass to obtain a wet film; the rotation speed of the spin coating is 3800-4000 r/min, and the spin coating time is 40-60 s;
s2-3, baking the wet film obtained in the step S2-2 to obtain a carbon-doped carbon nitride film electrode;
the solvent II is one or more of ethanol, polyvinyl alcohol and perfluorosulfonic acid.
2. The process according to claim 1, wherein the solvent I is water.
3. The preparation method according to claim 1, wherein in the step S1-2, the calcination process is specifically: heating to 400-550 ℃ at the speed of 2-4 ℃/min, and calcining for 3-6 h.
4. The production method according to any one of claims 1 to 3, wherein in the step S2-1, the solvent II is one or more of ethanol, polyvinyl alcohol and perfluorosulfonic acid; the frequency of the ultrasonic wave is 5-10 kHz, and the time of the ultrasonic wave is 3-5 min.
5. The method according to any one of claims 1 to 3, wherein in the step S2-2, the pretreatment process is specifically: and (3) sequentially washing the tin dioxide transparent conductive glass with water, ethanol and acetone for 2-3 times respectively.
6. The preparation method according to any one of claims 1 to 3, wherein the step S2-3 is specifically: and (3) baking the wet film at the temperature of 140-150 ℃ for 10min to obtain the carbon-doped carbon nitride film electrode.
7. The method of any one of claims 1 to 3, further comprising repeating steps S2-2 and S2-3 until a thickness of the carbon-doped carbon nitride thin film electrode reaches a preset value.
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| CN108906111B (en) * | 2018-07-26 | 2020-10-27 | 湖南大学 | Self-assembly carbon nitride copolymerized photocatalytic composite material and preparation method and application thereof |
| 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 |
| 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 |
| 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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| WO2011135782A1 (en) * | 2010-04-26 | 2011-11-03 | パナソニック株式会社 | Method for reducing carbon dioxide |
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