CN110508310B - Preparation method of Z-type photoelectrode - Google Patents
Preparation method of Z-type photoelectrode Download PDFInfo
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- CN110508310B CN110508310B CN201910801223.0A CN201910801223A CN110508310B CN 110508310 B CN110508310 B CN 110508310B CN 201910801223 A CN201910801223 A CN 201910801223A CN 110508310 B CN110508310 B CN 110508310B
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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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method of a Z-shaped photoelectrode, which comprises the steps of pretreating a pure titanium sheet to obtain a substrate material, preparing a titanium dioxide nanobelt array photoelectrode in situ from the substrate material by adopting a constant-pressure anodic oxidation method, adding melamine into ethylene glycol to obtain a modifying liquid, coating the modifying liquid on the surface of the titanium dioxide nanobelt array photoelectrode to obtain a composite photoelectrode, taking out the composite photoelectrode, placing the composite photoelectrode into a corundum boat with a cover, carrying out heat treatment and cooling to obtain the titanium dioxide nanobelt array photoelectrode with lamellar graphite phase carbon nitride and different crystal structures, repeating the steps to obtain the Z-shaped photoelectrode with controllable layers. Reduces the recombination of photo-generated electron holes, and is an environment-friendly material with visible light response and high photocatalytic activity.
Description
Technical Field
The invention relates to the technical field of composite photoelectrode preparation, in particular to a preparation method of a Z-shaped photoelectrode.
Background
Titanium dioxide as a conventional n-type semiconductor photocatalyst due to its superior optical and electronic propertiesThe photocatalyst has the advantages of stable physical and chemical properties, no toxic or side effect, low price, easy obtainment and the like, is widely researched and applied in the field of photocatalysis, and is the most researched photocatalyst material at present. However, titanium dioxide (TiO) 2 ) The photocatalyst has the following disadvantages: the recombination rate of the photo-generated electrons and the holes is higher; due to TiO 2 The forbidden band width is wide (3.2 eV), so that the ultraviolet light with energy larger than that of the forbidden band width can be absorbed only, and the utilization rate of the sunlight is low. To improve the above-mentioned defect to TiO 2 The photocatalyst is modified, the modification method mainly has the functions of noble metal doping, nonmetal doping, semiconductor compounding and surface sensitization, the semiconductor compounding effect is better compared with other modification methods, and the compounding method is diversified.
The carbon nitride has five allotropes, of which graphite phase carbon nitride (g-C) 3 N 4 ) Is the most stable one of the five carbon nitrides. The nanometer material is environment-friendly, non-toxic, cheap and easily available, belongs to a narrow-bandgap semiconductor, has the bandgap width of about 2.7eV, and has the maximum absorption wavelength of about 460nm, so that the nanometer material can effectively absorb visible light and has higher utilization efficiency on sunlight. At the same time, g-C 3 N 4 And has the advantages of good thermal stability, electronic and optical properties and the like. g-C according to the above-mentioned series of excellent characteristics 3 N 4 Great attention has been paid to the degradation of organic contaminants under visible light. However, graphite-phase carbon nitride obtained by a thermal polymerization method has the disadvantages of rapid recombination of photo-generated electrons and holes, and the like, and the photocatalytic efficiency is still to be improved. The narrow-band-gap semiconductor graphite-phase carbon nitride is compounded with the wide-band-gap titanium dioxide, so that the visible light absorption range can be improved, the migration of photo-generated electron holes is promoted, and the photocatalyst has high redox capability and finally excellent photocatalytic redox performance.
The current research only focuses on the preparation of graphite phase carbon nitride/titanium dioxide nanotube array photoelectrode and graphite phase carbon nitride/titanium dioxide powder, and no relevant report is found yet on the in-situ generation of the Z-shaped graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode through thermal polycondensation. The graphite phase carbon nitride/titanium dioxide nanotube array photoelectrode has the advantages of convenient recycling and low cost, but the graphite phase carbon nitride/titanium dioxide array photoelectrode prepared by the method has several defects, the generated graphite phase carbon nitride is deposited on the top of the nanotube in a quantum dot mode, the utilization rate of visible light and the adsorption quantity of pollutants are low, and the photocatalytic efficiency is reduced; the amount of graphite-phase carbon nitride deposited on the titanium dioxide photoelectrode by an anodic oxidation method and a chemical vapor deposition method is very small, and the absorption of visible light and the separation rate of photo-generated electrons and holes are not obviously improved; the separation of graphite phase carbon nitride/titanium dioxide powder from the suspension is costly and severely hampers the practical use of the process in contaminant treatment.
Disclosure of Invention
The invention provides a preparation method of a Z-type photoelectrode, which is characterized in that a titanium dioxide nanoribbon array is modified by graphite-phase carbon nitride to prepare the Z-type graphite-phase carbon nitride titanium dioxide nanoribbon array photoelectrode, and the Z-type graphite-phase carbon nitride titanium dioxide nanoribbon array photoelectrode has higher yield and separation efficiency of photo-generated electron holes, higher visible light utilization performance and obvious effect on photocatalytic degradation of antibiotic tetracycline hydrochloride (TC).
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a Z-type photoelectrode comprises the following steps:
s1: pretreating a pure titanium sheet to obtain a substrate material;
s2: preparing a titanium dioxide nanoribbon array photoelectrode in situ by a substrate material by adopting a constant-pressure anodic oxidation method;
s3: adding melamine into ethylene glycol, and uniformly mixing to obtain a modification liquid;
s4: uniformly coating the modifying liquid on the surface of the titanium dioxide nanobelt array photoelectrode, and drying to obtain a composite photoelectrode;
s5: taking out the amorphous composite photo-electrode, putting the composite photo-electrode into a corundum boat with a cover, carrying out heat treatment, and cooling along with a furnace to obtain a lamellar graphite phase carbon nitride and titanium dioxide nanobelt array photo-electrode with different crystal structures;
s6: and repeating the steps S4 to S5 to obtain the Z-shaped photoelectrode with controllable layers, namely the Z-shaped graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode.
Preferably, in step S1, the pretreatment includes, but is not limited to, cleaning, grinding, polishing, and ultrasonic cleaning.
Preferably, the cleaning solution adopted in the cleaning process is hydrofluoric acid, 600-mesh, 1000-mesh and 2000-mesh abrasive paper are adopted in the grinding and polishing process in sequence, and the ultrasonic cleaning solutions are water respectively; the ultrasonic cleaning method comprises the following steps of mixing ethanol, acetone and water, wherein the volume ratio of the ethanol to the acetone is 1:1, and carrying out ultrasonic cleaning for 10-20 min.
Preferably, in the step S2, the temperature is kept constant for 0.5 to 1 hour before anodizing, and the electrolyte is 0.25 to 0.75 percent of NH 4 F and 90-99% of glycol, the reaction temperature is 15-25 ℃, the voltage is 55-65V, and the oxidation time is 2-4 h.
Preferably, stirring is continuously carried out in the constant-pressure anodic oxidation process, the stirring speed is 600rpm/min, and the titanium dioxide nanobelt array photoelectrode is generated on the surface of the substrate material in situ.
Preferably, in the step S3, 0.05 to 2g of melamine is added into 5mL of ethylene glycol, and the mixture is stirred and mixed uniformly at 70 to 80 ℃, wherein the concentration of the melamine is 10 to 400 g/L.
Preferably, in the step S4, the modifying solution is uniformly coated on the surface of the titanium dioxide nanoribbon array photoelectrode by using a fur brush, and the surface is dried at the temperature of 210-220 ℃ for 10-15min to remove the ethylene glycol.
Preferably, in the step S5, the temperature is raised from room temperature to 450-650 ℃ at a temperature raising rate of 2-3 ℃/min under a nitrogen atmosphere, and the heat treatment is carried out for 1-3 h.
Preferably, the number of applications is 1-9.
The invention has the beneficial effects that:
the Z-type graphite phase carbon nitride nanosheet/titanium dioxide nanobelt array photoelectrode is conveniently prepared in situ, is economic and environment-friendly, has good repeatability, is easy to control the operation process, has mild conditions, overcomes the defects of the titanium dioxide nanobelt array and the graphite phase carbon nitride, widens the spectrum absorption range, reduces the recombination of photoproduction electron holes, and is an environment-friendly material with visible light response and high photocatalytic activity.
Drawings
FIG. 1 is an X-ray diffraction pattern of a graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode prepared in example one, with the abscissa representing the X-ray diffractometer scanning the entire diffraction area at an angle of 2 θ and the ordinate representing the unit of relative intensity.
Fig. 2(b), 2(d) and 2(c) are a scanning electron microscope image, a transmission electron microscope image and a high power transmission electron microscope image, respectively, of the graphite-phase carbon nitride/titanium dioxide nanoribbon array photoelectrode prepared in example two, and fig. 2(a) and 2(e) are a scanning electron microscope image and a transmission electron microscope image, respectively, of the titanium dioxide nanoribbon array photoelectrode of comparative example.
FIG. 3 shows a graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode, and comparative titanium dioxide nanoribbon array photoelectrode (TNBs), and a graphite phase carbon nitride photoelectrode (g-C) prepared in example two 3 N 4 ) The abscissa of the diagram shows the wavelength in nm and the ordinate shows the absorbance.
FIG. 4 is a schematic representation of photoluminescence from a graphite-phase carbon nitride/titania nanoribbon array photoelectrode prepared in example two, and from comparative titania nanoribbon array photoelectrodes (TNBs), with the abscissa representing wavelength in nm.
Fig. 5 is a graph showing the degradation performance of the graphite-phase carbon nitride/titanium dioxide nanoribbon array photoelectrode prepared in example two and the photocatalytic degradation tetracycline hydrochloride of a comparative titanium dioxide nanoribbon array photoelectrode (TNBs) under the irradiation of visible light, wherein the abscissa represents time in min, and the ordinate represents the degradation rate in%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The first embodiment is as follows:
a preparation method of a Z-type photoelectrode comprises the following steps:
1) cutting pure titanium sheets (Ti > 99.9%) into strip-shaped foils with the size of 100 multiplied by 10 multiplied by 0.2mm, cleaning by hydrofluoric acid, grinding and polishing by 600-mesh, 1000-mesh and 2000-mesh sandpaper, and respectively adding the pure titanium sheets into deionized water and acetone: ultrasonically cleaning the titanium dioxide nanoribbon array in ethanol at a ratio of 1:1(vol) and deionized water for 10min, and then placing the titanium dioxide nanoribbon array in the deionized water for sealing to obtain the base material for preparing the titanium dioxide nanoribbon array by anodic oxidation.
2) Taking a substrate material as a substrate, preparing a titanium dioxide nanobelt array in situ by adopting a constant-pressure anodic oxidation method, keeping the constant temperature for 0.5h before anodic oxidation, and using 0.5% NH as electrolyte 4 And F and 93% ethylene glycol, wherein the reaction temperature is 20 ℃, the voltage is 60V, the oxidation time is 2.5h, the mixture is continuously stirred in the constant-pressure anodic oxidation process, the stirring speed is 600rpm/min, the titanium dioxide nanoribbon array photoelectrode is generated in situ on the surface of the substrate material, and a large amount of deionized water is used for washing the surface of the photoelectrode immediately after the oxidation.
3) 2g of melamine is added into 5mL of ethylene glycol, stirred and mixed uniformly at 70 ℃, and the concentration of the melamine is 50g/L, so that the modification liquid is obtained.
4) Uniformly coating the modification liquid on the surface of the titanium dioxide nanobelt array photoelectrode by using a soft brush, drying at 210 ℃ for 10min, and volatilizing the glycol at the drying temperature.
5) And after drying, taking out the amorphous composite photo-electrode, putting the composite photo-electrode into a corundum boat with a cover, heating the composite photo-electrode to 550 ℃ from room temperature at a heating rate of 2 ℃/min in a nitrogen atmosphere, carrying out heat treatment for 2h, and cooling along with the furnace to obtain the lamellar graphite phase carbon nitride and titanium dioxide nanoribbon array photo-electrode with different crystal structures.
6) And (5) repeating the steps from 4) to 5) for 7 times to obtain the Z-shaped photoelectrode with controllable layers, namely the graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode.
Example two:
parts of this embodiment that are the same as those of the first embodiment are not described again, except that:
repeating the steps 4) to 5) for 5 times, namely coating 5 times.
Example three:
parts of this embodiment that are the same as those of the first embodiment are not described again, except that:
in step 5), the temperature is raised from room temperature to 500 ℃.
Example four:
parts of this embodiment that are the same as those of the first embodiment are not described again, except that:
the amount of melamine added was 0.5 g.
Test and experiment:
mixing 4cm 2 The sample is immersed in 40mL tetracycline hydrochloride solution with the concentration of 20mg/L and is continuously subjected to stirring dark treatment for 30min, a 150W xenon lamp with the wavelength of 420-780nm is used, the sample is subjected to photolysis for 60min, and data are recorded by a spectrophotometer test, and titanium dioxide nanobelt array photoelectrode (TNBs) which is not loaded by graphite phase carbon nitride nanosheets is used as a comparative example.
Example one X-ray diffraction pattern of the prepared graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode as shown in fig. 1, it can be seen that the graphite phase carbon nitride/titanium dioxide nanoribbon array is pure anatase phase titanium dioxide, the diffraction peak at 28.0 ° is due to stacking of characteristic layers of the aromatic system, and the distance between each layer is 0.318nm, and further the diffraction peak is proved to be the (002) crystal face (d) of graphite phase carbon nitride 002 0.322nm) belonging to the layered packing structure of hexagonal phase-like graphite materials.
Scanning electron micrographs and high resolution transmission electron micrographs of the graphite-phase carbon nitride/titanium dioxide nanoribbon array photoelectrode prepared in example two, and the comparative titanium dioxide nanoribbon array photoelectrode (TNBs) are shown in fig. 2. As can be seen from the figure, the photoelectrode prepared in the second example has a 1-dimensional belt-shaped surface and a bottom 3-dimensional nano tubular structure, wherein the nano bandwidth is about 20-100nm, the length can reach dozens of microns, and the surface of the titanium dioxide nano belt presents well-defined g-C 3 N 4 A thin layer, which morphology may be beneficial for increasing the specific surface area. The high-resolution transmission electron microscope also shows that g-C 3 N 4 With TiO 2 There is a heterojunction between the two crystals, the lattice spacing of the crystals is 0.35, 0.23 and 0.32nm, respectively, corresponding to TiO 2 (101) (001) and g-C 3 N 4 (002) The crystal face can enhance the response of visible light, promote the separation of photoinduced electron-hole pairs and improve the photocatalytic performance.
Example two prepared graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode (g-C) 3 N 4 TNBs), and comparative titanium dioxide nanoribbon array photoelectrodes (TNBs), and graphite phase carbon nitride photoelectrodes (g-C) 3 N 4 ) The light absorption properties of (a) are shown in FIG. 3. g-C 3 N 4 The absorption performance of the TNBs in ultraviolet and visible regions is obviously stronger than that of the TNBs, and g-C is 500nm later 3 N 4 The light absorption intensity of/TNBs was higher than that of UV, indicating g-C 3 N 4 The visible light absorption performance of the titanium dioxide photoelectrode is obviously improved, so that the visible light utilization rate of the graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode is improved.
Example two prepared graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode (g-C) 3 N 4 TNBs), and photoluminescence of comparative titanium dioxide nanoribbon array photoelectrode (TNBs) as shown in fig. 4. g-C 3 N 4 The PL intensity of/TNBs was lower than that of TNBs, indicating that g-C 3 N 4 The recombination amount of photogenerated electron holes of/TNBs is low. Indicates g-C 3 N 4 Hole generated by conduction band and TiO 2 Electrons generated by the valence band are compounded to release low-energy fluorescence and leave g-C with strong reducing capability 3 N 4 TiO with strong conduction band electron and oxidation ability 2 The valence band hole of (3) is reacted.
Example two prepared graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode (g-C) 3 N 4 TNBs), and a graph showing the degradation performance of photocatalytic degradation of tetracycline hydrochloride by a comparative titanium dioxide nanoribbon array photoelectrode (TNBs) under visible light irradiation, as shown in fig. 5. TNBs and g-C as degradation time increases 3 N 4 The photocatalytic degradation rate of/TNBs increased gradually, and the removal rate of TNBs increased slowly after 60 min. TNBs and g-C 3 N 4 The TC removal rates of the TNBs under 120min photodegradation conditions are respectively 30.66 percent and 46.34 percent, and g-C 3 N 4 The photocatalytic performance of the TNBs was 1.51 times higher than that of TNBs. The results show that g-C 3 N 4 And TiO 2 The heterojunction formed between the two obviously promotes the photocatalytic performance of the photoelectrode.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
Claims (7)
1. A preparation method of a Z-type photoelectrode is characterized by comprising the following steps:
s1: pretreating a pure titanium sheet to obtain a substrate material;
s2: preparing a titanium dioxide nanoribbon array photoelectrode in situ by a substrate material by adopting a constant-pressure anodic oxidation method;
s3: adding 0.05-2g of melamine into 5mL of ethylene glycol, stirring and uniformly mixing at 70-80 ℃, wherein the concentration of the melamine is 10-400g/L, and obtaining a modification liquid;
s4: uniformly coating the modification liquid on the surface of the titanium dioxide nanobelt array photoelectrode by using a soft brush, and drying at the temperature of 210-220 ℃ for 10-15min to remove ethylene glycol to obtain a composite photoelectrode;
s5: taking out the amorphous composite photo-electrode, putting the composite photo-electrode into a corundum boat with a cover, carrying out heat treatment, and cooling along with a furnace to obtain a lamellar graphite phase carbon nitride and titanium dioxide nanobelt array photo-electrode with different crystal structures;
s6: and repeating the steps S4 to S5 to obtain the Z-shaped photoelectrode with controllable layers, namely the Z-shaped graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode.
2. The method according to claim 1, wherein in the step S1, the pretreatment includes hydrofluoric acid cleaning, grinding and polishing, and ultrasonic cleaning.
3. The preparation method according to claim 2, wherein 600 mesh, 1000 mesh and 2000 mesh sandpaper are adopted in the sanding and polishing process in sequence, and the solution for ultrasonic cleaning is water or a mixed solution consisting of ethanol, acetone and water, wherein the volume ratio of the ethanol to the acetone is 1:1, and the ultrasonic cleaning is carried out for 10-20 min.
4. The method according to claim 1, wherein in step S2, the temperature is maintained for 0.5-1h before anodizing, and the electrolyte is 0.25-0.75% NH 4 F and 90-99% of glycol, the reaction temperature is 15-25 ℃, the voltage is 55-65V, and the oxidation time is 2-4 h.
5. The preparation method according to claim 4, characterized in that the titanium dioxide nanoribbon array photoelectrode is generated in situ on the surface of the substrate material by continuously stirring in the constant-pressure anodic oxidation process at a stirring speed of 600 rpm/min.
6. The method as set forth in any one of claims 2 to 5, wherein the step S5 is a heat treatment for 1 to 3 hours at a heating rate of 2 to 3 ℃/min from room temperature to 450 ℃ and 650 ℃ in a nitrogen atmosphere.
7. The method according to claim 6, wherein the number of coating times is 1 to 9.
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