CN112371179A - Fe-doped ZnO nano film and preparation method and application thereof - Google Patents
Fe-doped ZnO nano film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Fe-doped ZnO nano film and a preparation method and application thereof, the invention provides a Fe-doped ZnO nano material successfully prepared on a GPET transparent conductive flexible substrate by a hydrothermal method, the photocatalysis performance of the Fe-doped ZnO nano material is researched, zinc nitrate hexahydrate, hexamethylenetetramine and ferric nitrate nonahydrate are taken as main reactants, and a thin ZnO seed crystal layer is firstly ion sputtered on the surface of the GPET of the flexible substrate; then preparing Fe-doped ZnO precursor solutions with different concentrations; and vertically placing the flexible substrate into a reaction solution, and growing the Fe-doped ZnO nano structure by a hydrothermal method to obtain the Fe-ZnO/GPET nano composite material capable of being used as a photocatalyst. The product obtained by the hydrothermal reaction has a special regular hexagonal nano rod-like structure, has a strong degradation effect on methylene blue solution, has a wide research prospect in the fields of environmental management and the like, and is suitable for large-area production and application.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of metal oxide semiconductor materials, and particularly relates to a Fe-doped ZnO nano film, and a preparation method and application thereof.
[ background of the invention ]
Zinc oxide (ZnO), which is an n-type semiconductor, is widely used as a photocatalyst for photocatalytic degradation of organic dyes due to its excellent characteristics, such as a wide band gap of 3.37eV, a high exciton binding energy of about 60meV, anisotropic growth, and environmental protection. However, ZnO inhibits photocatalytic efficiency due to the rapid recombination of photogenerated electron-hole pairs. For nanomaterials, doping can result in significant changes in their properties, since the number of atoms after doping is small and the majority is at the surface of the nanomaterial.
The existing synthesis method of the ZnO nano material comprises an evaporation method, a sol-gel method, an atomic layer deposition method, a vapor deposition method, a spray pyrolysis method, a hydrothermal method and the like, is widely applied based on the advantages of simple preparation, large-scale production and the like of the hydrothermal method, and is an ideal approach for preparing the doped ZnO nano material.
At present, the preparation of the Fe-doped ZnO mostly involves similar to the present invention: like ACS OMEGA 4(2019)10252, the synthesis of Fe doped ZnO/reduced graphene oxide for gas sensing applications by hydrothermal method was mainly studied; the Journal of The Electrochemical Society 163(2016)517 is a document, and The successful preparation of ZnO nanospheres with different Fe doping concentrations by a hydrothermal method is mainly researched, so that The ZnO nanospheres are applied to a ZnO gas sensor for detecting formaldehyde. However, the above-mentioned conventional techniques do not provide a method for avoiding the inhibition of photocatalytic efficiency by ZnO and making full use of the semiconductor characteristics of ZnO.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a Fe-doped ZnO nano film and a preparation method and application thereof, so as to solve the problem that how to avoid the ZnO to inhibit the photocatalytic efficiency in the application process is lacked in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the Fe-doped ZnO nano film consists of Fe-doped ZnO nano rods, and the Fe-doped ZnO nano rods are attached to the GPET film.
A preparation method of a Fe-doped ZnO nano film comprises the following steps:
step 1, preprocessing a GPET flexible substrate;
step 3, preparing a precursor solution, wherein solutes of hexamethylenetetramine, zinc nitrate hexahydrate and ferric nitrate nonahydrate in the precursor solution are water; the molar ratio of hexamethylene tetramine to zinc nitrate hexahydrate to ferric nitrate nonahydrate is 1:1 (1-8);
and 4, placing the substrate deposited with the seed layer in a precursor solution, wherein the ZnO seed is vertical to the horizontal plane to form a reaction system, carrying out hydrothermal reaction on the reaction system, and generating the Fe-doped ZnO nano film on the GPET flexible substrate after the hydrothermal reaction.
The invention is further improved in that:
preferably, the pretreatment process in step 1 is as follows: cutting the GPET flexible substrate into a plurality of square substrates, sequentially ultrasonically cleaning the square substrates through acetone and ethanol, ultrasonically cleaning the square substrates through deionized water, and drying the cleaned square substrates for later use.
Preferably, in the step 2, the sputtering time is 3-5 min, the sputtering current is 6-10 mA, and the pressure is 8-10 Pa.
Preferably, in step 2, the thickness of the seed layer is 30 nm.
Preferably, in the step 3, the molar concentrations of the hexamethylenetetramine and the zinc nitrate hexahydrate are both 0.05mol/L, and the molar concentration of the ferric nitrate nonahydrate is 0.05-0.4 mol/L;
preferably, in the step 4, the hydrothermal reaction temperature is 90-100 ℃, and the hydrothermal reaction time is 5-7 h.
Preferably, in step 4, taking out the product after the hydrothermal reaction, cleaning the product, and drying at 60 ℃ for 1h to generate the Fe-doped ZnO nano film on the GPET flexible substrate.
The application of the Fe-doped ZnO nano film as a photocatalyst in photocatalytic degradation of methylene blue is characterized in that the GPET film attached with the Fe-doped ZnO nano film is placed in a methylene blue solution to form a catalytic system, the whole catalytic system is placed under a xenon lamp, and the GPET film attached with the Fe-doped ZnO nano film photocatalytically degrades the methylene blue.
Preferably, the power of the xenon lamp is 500W.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a Fe-doped ZnO nano film, which is characterized in that a hydrothermal method is adopted to successfully prepare a Fe-doped ZnO nano material on a GPET transparent conductive flexible substrate, zinc nitrate hexahydrate, hexamethylenetetramine and ferric nitrate nonahydrate are used as main reactants in the preparation method, a very thin ZnO seed crystal layer is firstly subjected to ion sputtering on the surface of the GPET flexible substrate, so that after ZnO grows up in a rod-shaped form, a thin oxidation film is formed on a compact ZnO nano rod, the problems of lattice mismatch, thermal mismatch and the like of the substrate and the Fe-doped ZnO nano film can be relieved, and on the other hand, ZnO is used as a seed crystal to perform induced nucleation, so that the hydrothermal growth of the zinc oxide nano rod is facilitated; then preparing Fe-doped ZnO precursor solutions with different concentrations; the flexible substrate is vertically placed in a reaction solution, a Fe-doped ZnO nano structure grows by a hydrothermal method, the ZnO nano structure grows into a nano rod-shaped structure with a cross section being a regular hexagon by Fe doping, the growth directions are not consistent, Fe-doped ZnO nano rods all grow obliquely along the substrate, and the hydrothermal method in the preparation process is low in production cost and easy to control ideal proportion and structural form of products.
The invention also discloses a Fe-doped ZnO nano film, which is attached to the flexible substrate of polyethylene glycol terephthalate GPET, the product of the film has a special regular hexagonal nano rod-shaped structure, has stronger degradation effect on methylene blue solution, has wide research prospect in the fields of environmental management and the like, is suitable for large-area production and application, and the flexible substrate can also improve the degradation rate of Methylene Blue (MB). The Fe-doped ZnO nano film grown on the GPET has the advantages of good photoelectric characteristics, flexibility, light weight, easiness in large-area production, convenience in transportation and the like, and the GPET is provided with a layer of graphene on the surface of PET, so that the excellent performances of the graphene and a semiconductor material can be combined, the conduction of electrons between the graphene and the semiconductor material is realized, the band gap of the semiconductor material can be reduced, the recombination efficiency of electron holes is inhibited, and the photocatalytic performance of the semiconductor material is improved. The nano rod-shaped structure has relatively large specific surface area, the Fe-ZnO/GPET nano composite material which can be used as a photocatalyst is obtained, and the Fe-doped metal nano particles enhance the photocatalytic activity of ZnO and show synergistic effect.
The invention also discloses application of the Fe-doped ZnO nano film as a photocatalyst in photocatalytic degradation of methylene blue, the film delays combination of photo-generated electron-hole pairs, and the improvement of the photocatalytic performance benefits from the synergistic effect of ZnO and Fe metal particles. The degradation principle is as follows: when light irradiates on the semiconductor material with wide band gap, electrons can be excited to form photo-generated electron-hole pairs, so that organic pollutants can be degraded. Since the band gap of Fe is relatively narrow, an impurity level between the conduction band and the valence band of ZnO is formed, and thus, when the photocatalyst is irradiated with ultraviolet light, photon energy is higher than or equal to the band gap of Fe-doped ZnO/GPET, so that electrons are excited from the Valence Band (VB) to the Conduction Band (CB), and a positively charged hole is generated in the valence band. In one aspect, doped Fe3+The electron-hole recombination is blocked by trapping the electron in the conduction band of ZnO/GPET, and more superoxide radical negative ions (O) are generated2-) Therefore, the adsorption performance is better, the catalytic performance is higher, and the photocatalytic activity of the Fe-doped ZnO/GPET film is improved. On the other hand, the positively charged hole left in the valence band can react with water to form a highly reactive hydroxyl group (. OH). OH and O2-Reacts with dye (MB) adsorbed on ZnO/GPET nano photocatalyst to generate water (H)2O), carbon dioxide (CO)2) Leading to degradation and decoloration thereof; after Fe is doped, the recombination rate of photon-generated carriers is greatly inhibited, the separation of photon-generated electron-hole pairs is effectively promoted, and the improvement of the photocatalytic activity of the Fe-doped ZnO/GPET nano material is facilitated. Therefore, the Fe-doped ZnO/GPET nano film has better photocatalysis efficiency on methylene blue and higher photocatalysis activity under the synergistic action of ZnO and Fe metal particles in the catalyst, and has potential application value in solving the problem of water pollution caused by organic dye which is not biodegradable and wastewater thereof.
[ description of the drawings ]
FIG. 1 is an XRD pattern of undoped and Fe-doped ZnO/GPET nanocomposites after 6 hours reaction at 95 ℃;
FIG. 2 is an SEM image of undoped and Fe-doped ZnO/GPET nanocomposites after 6 hours reaction at 95 ℃;
FIG. 3 is a photoluminescence spectrum of undoped and Fe-doped ZnO/GPET nanocomposites;
FIG. 4 is the photodegradation rate of ultraviolet light for Methylene Blue (MB) in the presence of ZnO/GPET and FZO/GPET samples;
FIG. 5 is the change in absorption intensity of methylene blue in solution in the presence of FZO/GPET.
FIG. 6 is a schematic diagram of the generation and transfer of charges during the degradation process of a simulated methylene blue solution under the irradiation of ultraviolet light.
[ detailed description ] embodiments
The invention is described in further detail below with reference to the accompanying drawings:
in the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly and encompass, for example, both fixed and removable connections; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The preparation method of the Fe-doped ZnO nano film provided by the invention comprises the following steps:
firstly, cleaning a GPET flexible substrate, cutting the GPET flexible substrate into a square shape of 1.5cm multiplied by 1.5cm, carrying out ultrasonic cleaning with acetone (10min) and ethanol (10min), taking out, transferring into deionized water, carrying out ultrasonic cleaning again for 10min, taking out the GPET flexible substrate, putting into an oven, and drying at 70 ℃ for later use.
And a second step of seed crystal layer plating: and depositing a ZnO seed layer (30nm) on the dried GPET flexible substrate through a radio frequency magnetron sputtering instrument (taking high-purity Zn as a target), wherein the sputtering time is 3-5 min, the sputtering current is 6-10 mA, the sputtering is in a vacuum environment, and the vacuum degree is 8-10 Pa.
Thirdly, preparing a precursor solution: adding Hexamethylenetetramine (HMT) and zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) and iron nitrate nonahydrate (Fe (NO)3)3·9H2O) mixed solution of Hexamethylenetetramine (HMT) and zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) was 0.05mol/L in molar concentration, and ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) is 0.05-0.4mol/L, and is magnetically stirred for 10min until the precursor solution is completely dissolved to obtain the precursor solution. Zn (NO) in precursor solution3)2·6H2O、HMT、Fe(NO3)3·9H2The molar ratio of O is 1:1 (1-8).
Step four, preparing the Fe-doped ZnO nano film: the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, putting the GPET substrate into an oven to react for 5-7 h at a constant temperature of 90-100 ℃, growing a Fe-doped ZnO nano film with a nano structure, naturally cooling to room temperature, taking out the film, repeatedly cleaning the film with distilled water and absolute ethyl alcohol, drying the film for 1h at 60 ℃, and taking out the film to obtain a sample.
The fifth step of photocatalytic experiment: firstly, preparing a 2mg/L methylene blue solution for standby, and taking a small amount of rinsed FZO/GPET nano film (1.5cm multiplied by 1.5cm) to ensure that a sample can be well contacted with the methylene blue solution. The rinsed FZO/GPET nano-film was placed right side up in a photocatalytic reactor, while 30mL of methylene blue solution was added, and placed under a 500W xenon lamp (Miao gold Source, CEL-S500) to perform photocatalytic reaction by ultraviolet irradiation. Finally, the absorbance value of methylene blue solution (λ max equals 664 nm) is tested every 30min, so as to research the catalytic performance of the Fe-doped ZnO nano film.
The invention provides an application approach of a Fe-doped ZnO nano film, which comprises the following steps: and (3) degrading the methylene blue solution by photocatalysis. The specific process of photocatalytic degradation of methylene blue solution is as follows: carrying out photocatalytic reaction under a 500W xenon lamp through ultraviolet irradiation, taking the Fe-doped ZnO nano-film/GPET nano-composite material as a photocatalyst, and carrying out photocatalytic reaction by adopting a timing sampling determination and magnetic stirring mode.
The ZnO nano-film/GPET nano-composite material provided by the invention can be used as a stable photocatalyst, the photocatalytic activity is further improved by doping Fe, and a foundation is laid for researching the action of a ZnO semiconductor in the field of photocatalysis. Meanwhile, the preparation method is simple, expensive experimental equipment is not needed, the cost is greatly reduced, and large-area preparation can be carried out, so that the preparation method has a wide application prospect in the aspect of further popularization and production.
The invention will be described in more detail below with reference to the accompanying drawings and preferred embodiments of the invention.
Comparative example 1:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, and Fe (NO) is not contained3)3·9H2O, stirring for 20min by using a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
The XRD pattern of the reaction product obtained in the comparative example is shown in the upper curve of fig. 1, the SEM morphology is shown in fig. 2(a-b), and the pure ZnO nanostructure has a hexagonal rod shape.
Example 1:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2Molar ratio of O is 1:1:1, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.05mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 2:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:2, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.1mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 3:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:3, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.15mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 4:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution and precursorZn (NO) in solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:4, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.2mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
The XRD patterns of the reaction products obtained in the comparative example and example 4 are shown in the curves in fig. 1, except that the diffraction peak near 53.8 ° is derived from the GPET flexible substrate, and the other diffraction peaks are assigned to characteristic peaks of ZnO, which indicates that the ZnO nanostructures before and after Fe doping are hexagonal wurtzite structures. Meanwhile, no other impurity peaks appear in the XRD spectrogram, which indicates that the purity of the sample is high. In addition, the diffraction peak of the (002) crystal face of the sample is strongest, which indicates that ZnO arrays grown on GPET flexible substrates all have good C-axis preferred orientation. As shown in fig. 2(a) and 2(b), the Fe doping causes the ZnO nanostructure to grow into a nanorod structure with a cross section of a regular hexagon, the growth direction is not consistent, and most of the Fe-doped ZnO nanorods obliquely grow along the substrate and are densely distributed on the PET-ITO substrate. FIG. 3 is Photoluminescence (PL) spectra of ZnO/GPET and FZO/GPET nanomaterials. Compared with a ZnO/GPET nano material which is not doped with Fe, the ultraviolet light-emitting peak of the FZO/GPET is obviously weakened, which shows that after the Fe is doped, the recombination rate of photon-generated carriers is greatly inhibited, the separation of photon-generated electrons and photon-generated pairs is effectively promoted, and the photocatalytic activity of the FZO/GPET nano material is favorably improved. FIG. 4 is a graph showing the degradation rate of ZnO/GPET and FZO/GPET when the photocatalyst is irradiated for 4h by a xenon lamp. The photocatalytic activity of the FZO/GPET nano composite material is obviously better than that of the undoped ZnO/GPET nano composite material. Meanwhile, the adsorption effect of FZO/GPET photocatalysis on the MB solution under the condition of no illumination is analyzed, and the result shows that the adsorption degradation rate of the MB solution is only 6.61% at 240min, which is 36.14% lower than the degradation rate after illumination, and the fact shows that the photocatalytic degradation plays a key role in the above reaction. FIG. 5 shows the absorbance of MB solution catalyzed by FZO/GPET nano-film as a function of photocatalytic time. Since the absorbance of the MB solution is directly proportional to its concentration, it can be seen that its concentration gradually decreases with increasing photocatalytic time.
The photocatalytic performance of the ZnO nano film doped with 15% of Fe is researched: the undoped (comparative test) and Fe-doped ZnO nano films are respectively placed into a quartz tube with the length of 20cm, 30mL of methylene blue solution with the reaction concentration of 2mg/L is added, the mixture is irradiated for 300 minutes under a 500W xenon lamp, 2mL of samples are taken every 30min, and the change of the concentration of the methylene blue solution along with the reaction time is analyzed by a direct colorimetric method at the wavelength of 664 nm. The calculation formula of the degradation rate is as follows:
in the formula: c0Denotes the initial concentration of methylene blue solution, CtDenotes the concentration of the methylene blue solution at time t, A0Denotes the initial absorbance of the methylene blue solution, AtAnd (3) expressing the absorbance of the methylene blue solution at the time t, calculating the degradation rate of the methylene blue solution in each time period, and drawing a relation curve of the degradation rate and the time.
Example 5:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 9Pa, the current is maintained for 1min at 6mA, and the current is maintained for 3min at 10 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:5, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.25mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 6:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 8Pa, the current is kept for 5min at 6mA, and the current is kept for 4min at 7 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:6, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.3mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 7 hours at a constant temperature of 90 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 7:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:7, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.35mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 5 hours at a constant temperature of 100 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
Example 8:
1) plating a ZnO seed crystal layer on the surface of the GPET substrate by using an ion sputtering coating instrument, wherein the pressure is 10Pa, the current is maintained for 1min at 6mA, and the current is maintained for 4min at 8 mA;
2) preparing precursor solution, Zn (NO) in the precursor solution3)2·6H2O, HMT and Fe (NO)3)3·9H2The molar ratio of O is 1:1:8, Zn (NO)3)2·6H2The molar concentrations of O and HMT are both 0.05mol/L, Fe (NO)3)3·9H2The molar concentration of O is 0.4mol/L, and the mixture is stirred for 20min by a magnetic stirrer;
3) the resulting precursor solution was transferred to a 40mL closed stainless steel autoclave lined with polytetrafluoroethylene. And then vertically immersing the GPET substrate on which the ZnO seed layer is deposited into the precursor solution, then putting the GPET substrate into an oven to react for 6 hours at a constant temperature of 95 ℃, naturally cooling to room temperature, taking out the GPET substrate, repeatedly cleaning the GPET substrate with distilled water and absolute ethyl alcohol, drying the GPET substrate for 1 hour at a temperature of 60 ℃, and taking out the GPET substrate to obtain a sample.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The Fe-doped ZnO nano film is characterized by consisting of Fe-doped ZnO nano rods, wherein the Fe-doped ZnO nano rods are attached to a GPET film.
2. A preparation method of a Fe-doped ZnO nano film is characterized by comprising the following steps:
step 1, preprocessing a GPET flexible substrate;
step 2, depositing a ZnO seed layer on the GPET flexible substrate through magnetron sputtering to obtain a substrate deposited with a seed layer;
step 3, preparing a precursor solution, wherein solutes of hexamethylenetetramine, zinc nitrate hexahydrate and ferric nitrate nonahydrate in the precursor solution are water; the molar ratio of hexamethylene tetramine to zinc nitrate hexahydrate to ferric nitrate nonahydrate is 1:1 (1-8);
and 4, placing the substrate deposited with the seed layer in a precursor solution, wherein the ZnO seed is vertical to the horizontal plane to form a reaction system, carrying out hydrothermal reaction on the reaction system, and generating the Fe-doped ZnO nano film on the GPET flexible substrate after the hydrothermal reaction.
3. The method for preparing the Fe-doped ZnO nano-film according to claim 2, wherein the pretreatment process in the step 1 is as follows: cutting the GPET flexible substrate into a plurality of square substrates, sequentially ultrasonically cleaning the square substrates through acetone and ethanol, ultrasonically cleaning the square substrates through deionized water, and drying the cleaned square substrates for later use.
4. The method for preparing an Fe-doped ZnO nano-film according to claim 2, wherein in the step 2, the sputtering time is 3-5 min, the sputtering current is 6-10 mA, and the pressure is 8-10 Pa.
5. The method for preparing an Fe-doped ZnO nano-film according to claim 2, wherein in the step 2, the thickness of the seed layer is 30 nm.
6. The method for preparing an Fe-doped ZnO nano-film according to claim 2, wherein in the step 3, the molar concentrations of hexamethylene tetramine and zinc nitrate hexahydrate are both 0.05mol/L, and the molar concentration of iron nitrate nonahydrate is 0.05-0.4 mol/L.
7. The method for preparing an Fe-doped ZnO nano-film according to claim 2, wherein in the step 4, the hydrothermal reaction temperature is 90-100 ℃ and the hydrothermal reaction time is 5-7 h.
8. The method for preparing the Fe-doped ZnO nano-film according to claim 2, wherein in the step 4, the product is taken out after the hydrothermal reaction, the product is dried after being cleaned, the drying temperature is 60 ℃, the drying time is 1h, and the Fe-doped ZnO nano-film is generated on a GPET flexible substrate.
9. The use of the Fe-doped ZnO nanofilm of claim 1 as a photocatalyst for photocatalytic degradation of methylene blue, wherein the GPET film with the Fe-doped ZnO nanofilm attached thereto is placed in a methylene blue solution to form a catalytic system, and the whole catalytic system is placed under a xenon lamp, and the GPET film with the Fe-doped ZnO nanofilm attached thereto photocatalytically degrades methylene blue.
10. The application of the Fe-doped ZnO nano-film as a photocatalyst in photocatalytic degradation of methylene blue according to claim 9, wherein the power of the xenon lamp is 500W.
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