CN113832479B - Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photoelectric catalyst and preparation method thereof - Google Patents
Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photoelectric catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photoelectric catalyst and preparation method thereof, fe 2 O 3 (Ti) the nanoarray and 2-aminoterephthalic acid are well dispersed in DMF; placing the mixed solution in a hydrothermal reaction kettle lined with polytetrafluoroethylene, and carrying out hydrothermal reaction for 16-24 hours at the temperature of 100-140 ℃; fully washing a product in the hydrothermal reaction kettle by using DMF (dimethyl formamide) and ethanol, and drying the product in a vacuum drying oven to constant weight to obtain Fe with a core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst. The invention adopts a solvothermal method to prepare Fe 2 O 3 (Ti)@NH 2 MIL-101 (Fe) composite photocatalyst, the process of which is relatively simple; prepared Fe 2 O 3 (Ti)@NH 2 the-MIL-101 (Fe) composite photoelectric catalyst has controllable shell thickness and excellent photoelectric performance, and has obvious reference significance for developing photoelectrode materials for decomposing water to produce hydrogen.
Description
Technical Field
The invention belongs to the technical field of photoelectric catalytic materials, and particularly relates to Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst and a preparation method thereof.
Background
As the global environmental pollution and energy crisis problems caused by the excessive use of traditional fossil fuels increasingly threaten the survival and development of human beings, the search for clean and renewable energy sources is urgent. Hydrogen energy belongs to a clean energy source with high energy density, is generally considered as a main bridge for connecting fossil energy to renewable energy, however, hydrogen energy rarely exists on the earth independently, is often presented as a compound, and can be produced only by other energy conversion. The photoelectrocatalysis water decomposition hydrogen production is one of ideal ways for preparing hydrogen energy by utilizing solar energy, and the photoelectrocatalysis material is utilized to realize visible light driven water decomposition into hydrogen and oxygen under the assistance of illumination and a small amount of electric energy. Therefore, the significance of developing a photocatalyst is self-evident.
Fe 2 O 3 The band gap energy is 1.9-2.1eV, the coating is sensitive to visible light, the coating is rich in earth crust content, non-toxic, good in thermal stability and good in photoelectric property, and the coating becomes a subject of great attention of researchers. But Fe 2 O 3 The method also has certain defects such as short diffusion distance of photogenerated holes, low light absorption coefficient, short service life of photogenerated carriers and the like, and limits further application of the photogenerated carriers. In response to these deficiencies, researchers have made many investigations, such as element doping, deposition of noble metal promoters, and the like. Wherein the element doping is an increase of Fe 2 O 3 Conductivity and charge separation efficiency. Among the numerous doping elements, the Ti element is highly effective, but the increase is still limited with respect to the actual requirement. Researchers find that the surface reaction kinetic energy barrier of the material can be reduced by utilizing a method of depositing the noble metal promoter on the basis of the method, and the photoelectric property of the material can be further improved. However, another disadvantage of this method is the high cost of the precious metal. If the two methods can be used for making up for the deficiencies of the two methods, the cost is controlled, and the Fe can be obviously improved 2 O 3 The photoelectric property of the composite material has obvious research significance. The metal organic framework material which is combined by coordination bonds of metal atoms or clusters and organic ligands has larger specific surface area and good photocatalysis effect, and each metal cluster is a metalThe active sites are distributed in the whole material more evenly, and the cost is not high, thus being praised as an ideal cocatalyst.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides Fe 2 O 3 (Ti)@NH 2 a-MIL-101 (Fe) composite photoelectric catalyst and a preparation method thereof, and prepares a titanium-doped Fe with a core-shell structure 2 O 3 Metal organic frame material [ Fe ] 2 O 3 (Ti)@NH 2 -MIL-101(Fe)]The composite photoelectric catalyst has relatively simple process and good photoelectric performance, and has obvious reference significance for developing photoelectrode materials for preparing hydrogen by decomposing water.
The technical scheme adopted by the invention is as follows: fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst and a method for preparing the same, comprising the steps of:
s1: mixing Fe 2 O 3 (Ti) the nanoarray and 2-aminoterephthalic acid are fully dispersed in DMF, wherein the concentration of 2-aminoterephthalic acid is 10-50mmol/L;
s2: placing the mixed solution obtained in the step S1 into a hydrothermal reaction kettle lined with polytetrafluoroethylene, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at the temperature of 100-140 ℃ for 16-24 hours;
s3: fully washing a product in the hydrothermal reaction kettle by using DMF (dimethyl formamide) and ethanol, and drying the product in a vacuum drying oven to constant weight to obtain Fe with a core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst.
Further, fe in step S1 2 O 3 The (Ti) nanoarrays are rod-like structures with the average diameter of the rods being 45-55nm.
In particular, fe 2 O 3 The preparation steps of the (Ti) nano array are as follows:
S1.1：FeCl 3 ·6H 2 o and Na 2 SO 4 Fully dispersed in 20mL deionized water, and 0.05mmol TiCl is added dropwise 4 Placing the mixture in a hydrothermal reaction kettle lined with polytetrafluoroethylene, and then obliquely placing a conductive glass substrateIn the hydrothermal reaction kettle, the conductive side faces downwards;
s1.2: carrying out hydrothermal reaction on the hydrothermal reaction kettle for 4 hours in a forced air drying oven at the temperature of 120 ℃;
s1.3: after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, taking out a product in the hydrothermal reaction kettle, repeatedly washing the product to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight;
s1.4: placing the dried product in a muffle furnace, and keeping the temperature of the muffle furnace at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
The technical scheme adopted by the invention is as follows: fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst with Fe core 2 O 3 (Ti) shell is NH 2 MIL-101 (Fe), with an average shell thickness of 2-5nm.
Further, NH 2 The average thickness of the-MIL-101 (Fe) shell was 3.5nm.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts a solvothermal method to prepare Fe 2 O 3 (Ti)@NH 2 MIL-101 (Fe) composite photocatalyst, the process of which is relatively simple; prepared Fe 2 O 3 (Ti)@NH 2 the-MIL-101 (Fe) composite photoelectric catalyst has controllable shell thickness and good photoelectric performance, and has obvious reference significance for developing photoelectrode materials for preparing hydrogen by decomposing water.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product of example 1 of the present invention;
FIG. 2 is a scanning and transmission electron micrograph of the product of example 1 of the present invention;
FIG. 3 is a chart of the infrared spectrum of the product of example 1 of the present invention;
FIG. 4 is a linear sweep voltammogram of the product of example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1
Embodiments of the present invention provide a Fe 2 O 3 (Ti)@NH 2 A method for preparing an MIL-101 (Fe) composite photocatalyst, comprising the steps of:
s1: 0.27g of FeCl 3 ·6H 2 O (Beijing YinoKai science and technology Co., ltd., the same below) and 0.142g of Na 2 SO 4 (Yongda chemical reagents Co., ltd., tianjin, the same below) was thoroughly dispersed in 20mL of deionized water, and 0.05mmol of TiCl was slowly dropped into the solution under stirring 4 (Shanghai Michelin Biochemical technology Co., ltd., the same below), transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, obliquely placing a conductive glass (FTO) substrate in the hydrothermal reaction kettle with the conductive side facing downwards, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, repeatedly washing a product in the hydrothermal reaction kettle to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight. Placing the dried product in a muffle furnace, and keeping the temperature of the muffle furnace at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
The Fe obtained above 2 O 3 (Ti) the nanoarray and 0.036g of 2-aminoterephthalic acid (Shanghai Michelin Biochemical Co., ltd., the same below) were well dispersed in 20mL of nitrogen, nitrogen-Dimethylformamide (DMF) (Shanghai Michelin Biochemical Co., ltd., the same below), wherein the concentration of 2-aminoterephthalic acid was 10mmol/L.
S2: and (3) transferring the mixed solution obtained in the step (S1) to a hydrothermal reaction kettle lined with polytetrafluoroethylene, and keeping the hydrothermal reaction kettle in an air-blowing drying oven at 100 ℃ for 16 hours.
S3: and taking out the hydrothermal reaction kettle, naturally cooling to room temperature, fully washing a product in the hydrothermal reaction kettle by using DMF and ethanol, and drying in a vacuum drying oven at 70 ℃ to constant weight. Thus obtaining the Fe with the core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst.
Preparing 1mol/L KOH solution as electrolyte and Fe 2 O 3 (Ti)@NH 2 MIL-101 (Fe) is used as a working electrode, a Pt electrode is used as a counter electrode, hg/HgO is used as a reference electrode, and a three-electrode system photoelectrochemical test is carried out on a sample under AM 1.5G simulated sunlight. The results of the linear sweep voltammetry tests show that Fe 2 O 3 (Ti)@NH 2 Photocurrent density of the MIL-101 (Fe) complex sample was 4.24mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 6.01 times of the total weight of the powder.
As can be seen from FIG. 1, fe was produced 2 O 3 The (Ti) nanoarrays are consistent with standard card 33# -0664, indicating their high purity.
FIG. 2 depicts scanning and transmission electron micrographs of the product. As can be seen from FIG. 2 (a), fe 2 O 3 (Ti) the surface of the nanoarrays was relatively smooth, with the average diameter of the rods being about 50nm; as can be seen from FIG. 2 (b), fe 2 O 3 (Ti)@NH 2 Surface of MIL-101 (Fe) composite photocatalyst with respect to Fe 2 O 3 The (Ti) control sample became rough due to the outer layer being coated with a layer of NH 2 -MIL-101 (Fe) shell; as can be seen from FIG. 2 (c), fe 2 O 3 (Ti)@NH 2 the-MIL-101 (Fe) composite photocatalyst presents a remarkable core-shell structure, and the average thickness of the shell is about 2.5nm.
FIG. 3 depicts the infrared spectrum of the product. As can be seen from the figure, fe 2 O 3 (Ti) pure sample in 543cm -1 An absorption peak appears, which is caused by Fe-O, and Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst at 3400cm -1 And 1700cm -1 There appeared a diffraction peak due to the contribution of-O-H and C = O, respectively, confirming Fe laterally 2 O 3 (Ti)@NH 2 Successful preparation of MIL-101 (Fe).
FIG. 4 depicts a linear sweep voltammogram of the product. As can be seen, fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photoelectricityThe photocurrent density of the catalyst was 4.24mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 6.01 times of the total weight of the powder. This also indicates that the technique is an effective increase in Fe 2 O 3 (Ti) method of photoelectric properties.
Example 2
Embodiments of the present invention provide a Fe 2 O 3 (Ti)@NH 2 A method for preparing an MIL-101 (Fe) composite photocatalyst, comprising the steps of:
s1: 0.27g of FeCl 3 ·6H 2 O, 0.142g of Na 2 SO 4 Fully dispersed in 20mL deionized water, and slowly dropped with 0.05mmol TiCl under the stirring state 4 Then transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, transferring the mixed solution into the hydrothermal reaction kettle with the polytetrafluoroethylene lining, obliquely placing an FTO (fluorine-doped tin oxide) substrate in the hydrothermal reaction kettle with the conductive side facing downwards, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, repeatedly washing a product in the hydrothermal reaction kettle to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight. Placing the dried product in a muffle furnace, and keeping the dried product at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
Fe obtained above 2 O 3 (Ti) the nanoarray and 0.180g of 2-aminoterephthalic acid were well dispersed in 20mL of DMF, wherein the concentration of 2-aminoterephthalic acid was 50mmol/L.
S2: and (3) transferring the mixed solution obtained in the step (S1) to a hydrothermal reaction kettle lined with polytetrafluoroethylene, and keeping the hydrothermal reaction kettle in a forced air drying oven at 140 ℃ for 24 hours.
S3: and taking out the hydrothermal reaction kettle, naturally cooling to room temperature, fully washing a product in the hydrothermal reaction kettle by using DMF and ethanol, and drying in a vacuum drying oven at 70 ℃ to constant weight. Fe with a core-shell structure can be obtained 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) complexationA photo-catalyst.
The scanning transmission electron microscope shows that Fe 2 O 3 (Ti) the average diameter of the core layer of the array is kept constant at about 50nm; fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) shell thickness increase, average shell thickness of about 5nm. The same photoelectrochemical test as in example 1 was carried out, and the results of the linear sweep voltammetry test showed Fe 2 O 3 (Ti)@NH 2 Photocurrent density of the MIL-101 (Fe) complex sample was 2.16mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 3.06 times of the total weight of the powder.
Example 3
Embodiments of the present invention provide a Fe 2 O 3 (Ti)@NH 2 A method for preparing an MIL-101 (Fe) composite photocatalyst, comprising the steps of:
s1: 0.27g of FeCl 3 ·6H 2 O, 0.142g of Na 2 SO 4 Fully dispersed in 20mL of deionized water, and 0.05mmol of TiCl is slowly dropped in the deionized water under the stirring state 4 Then transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, transferring the mixed solution into the hydrothermal reaction kettle with the polytetrafluoroethylene lining, obliquely placing an FTO (fluorine-doped tin oxide) substrate in the hydrothermal reaction kettle with the conductive side facing downwards, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, repeatedly washing a product in the hydrothermal reaction kettle to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight. Placing the dried product in a muffle furnace, and keeping the dried product at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
The Fe obtained above 2 O 3 (Ti) the nanoarray and 0.072g of 2-aminoterephthalic acid were well dispersed in 20mL of DMF, wherein the concentration of 2-aminoterephthalic acid was 20mmol/L.
S2: and (3) transferring the mixed solution obtained in the step (S1) to a hydrothermal reaction kettle lined with polytetrafluoroethylene, and keeping the hydrothermal reaction kettle in an air-blowing drying oven at 110 ℃ for 18 hours.
S3: and taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, fully washing a product in the hydrothermal reaction kettle by using DMF (dimethyl formamide) and ethanol, and drying the product in a vacuum drying oven at 70 ℃ to constant weight. Thus obtaining the Fe with the core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst.
The scanning transmission electron microscope shows that Fe 2 O 3 (Ti) the average diameter of the core layer of the array is kept constant at about 50nm; fe 2 O 3 (Ti)@NH 2 The MIL-101 (Fe) shell thickness varied, with an average shell thickness of about 3.5nm. The same photoelectrochemical test as in example 1 was carried out, and the results of the linear sweep voltammetry test showed Fe 2 O 3 (Ti)@NH 2 The photocurrent density of the MIL-101 (Fe) complex sample was 7.18mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 10.18 times of.
Example 4
Embodiments of the present invention provide a Fe 2 O 3 (Ti)@NH 2 A method for preparing an MIL-101 (Fe) composite photocatalyst, comprising the steps of:
s1: 0.27g of FeCl 3 ·6H 2 O, 0.142g of Na 2 SO 4 Fully dispersed in 20mL deionized water, and slowly dropped with 0.05mmol TiCl under the stirring state 4 Then transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, transferring the mixed solution into the hydrothermal reaction kettle with the polytetrafluoroethylene lining, obliquely placing an FTO (fluorine-doped tin oxide) substrate in the hydrothermal reaction kettle with the conductive side facing downwards, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours. And after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, repeatedly washing a product in the hydrothermal reaction kettle to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight. Placing the dried product in a muffle furnace, and keeping the dried product at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
The Fe obtained above 2 O 3 (Ti) the nanoarray and 0.108g of 2-aminoterephthalic acid were well dispersed in 20mL of DMF, wherein the concentration of 2-aminoterephthalic acid was 30mmol/L.
S2: and (3) transferring the mixed solution obtained in the step (S1) to a hydrothermal reaction kettle lined with polytetrafluoroethylene, and keeping the hydrothermal reaction kettle in an air-blowing drying oven at 120 ℃ for 20 hours.
S3: and taking out the hydrothermal reaction kettle, naturally cooling to room temperature, fully washing a product in the hydrothermal reaction kettle by using DMF and ethanol, and drying in a vacuum drying oven at 70 ℃ to constant weight. Thus obtaining the Fe with the core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst.
The scanning transmission electron microscope shows that Fe 2 O 3 (Ti) the average diameter of the core layer of the array is kept constant at about 50nm; fe 2 O 3 (Ti)@NH 2 The MIL-101 (Fe) shell thickness varied, with an average shell thickness of about 4nm. The same photoelectrochemical test as in example 1 was carried out, and the results of the linear sweep voltammetry test showed Fe 2 O 3 (Ti)@NH 2 The photocurrent density of the MIL-101 (Fe) complex sample was 5.05mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 7.16 times of.
Example 5
Embodiments of the present invention provide a Fe 2 O 3 (Ti)@NH 2 A method for preparing an MIL-101 (Fe) composite photocatalyst, comprising the steps of:
s1: 0.27g of FeCl 3 ·6H 2 O, 0.144g of Na 2 SO 4 Fully dispersed in 20mL deionized water, and slowly dropped with 0.05mmol TiCl under the stirring state 4 Then transferring the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, transferring the mixed solution into the hydrothermal reaction kettle with the polytetrafluoroethylene lining, obliquely placing an FTO (fluorine-doped tin oxide) substrate in the hydrothermal reaction kettle with the conductive side facing downwards, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours. After the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, and producing the product in the hydrothermal reaction kettleThe material was repeatedly washed with ethanol and deionized water to neutrality, and then dried in a forced air drying oven at 70 ℃ to constant weight. Placing the dried product in a muffle furnace, and keeping the dried product at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nanoarrays.
The Fe obtained above 2 O 3 (Ti) the nanoarray and 0.180g of 2-aminoterephthalic acid were well dispersed in 20mL of DMF, wherein the concentration of 2-aminoterephthalic acid was 40mmol/L.
S2: and (3) transferring the mixed solution obtained in the step (S1) to a hydrothermal reaction kettle lined with polytetrafluoroethylene, and maintaining the hydrothermal reaction kettle in a forced air drying oven at 130 ℃ for 22 hours.
S3: and taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, fully washing a product in the hydrothermal reaction kettle by using DMF (dimethyl formamide) and ethanol, and drying the product in a vacuum drying oven at 70 ℃ to constant weight. Fe with a core-shell structure can be obtained 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst.
The scanning transmission electron microscope shows that Fe 2 O 3 (Ti) the average diameter of the core layer of the array is kept constant at about 50nm; fe 2 O 3 (Ti)@NH 2 The MIL-101 (Fe) shell thickness varied, with an average shell thickness of about 4.5nm. The same photoelectrochemical test as in example 1 was carried out, and the results of the linear sweep voltammetry test showed Fe 2 O 3 (Ti)@NH 2 The photocurrent density of the-MIL-101 (Fe) complex sample was 3.02mA/cm 2 Is Fe 2 O 3 (Ti) control 0.705mA/cm 2 4.28 times of.
As can be seen from examples 1 to 5, NH was encapsulated in a certain thickness range 2 The MIL-101 (Fe) shell layer can increase Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) photocurrent density, but beyond a certain thickness, the photocurrent density would drop instead. Under the condition of illumination, fe 2 O 3 (Ti) photo-excited generation of photo-generated holes and electrons, ultra-thin NH 2 MIL-101 (Fe) can transfer part of photogenerated holes, thereby realizing the separation of photogenerated holes and electronsThereby enhancing the photocurrent density thereof.
The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of protection of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teaching of the technical solutions of the present invention, should be considered to be within the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention or equivalent technical solutions designed to achieve the above technical effects are also within the scope of the present invention.
Claims (2)
1. Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst, characterized in that: the method comprises the following steps:
s1: mixing Fe 2 O 3 (Ti) the nanoarray and 2-amino terephthalic acid are fully dispersed in DMF, wherein the concentration of the 2-amino terephthalic acid is 10-30mmol/L;
Fe 2 O 3 the preparation steps of the (Ti) nano array are as follows:
s1.1:0.27g FeCl 3 •6H 2 O and 0.142g of Na 2 SO 4 Fully dispersed in 20mL deionized water, and 0.05mmol TiCl is added dropwise 4 Placing the mixture in a hydrothermal reaction kettle lined with polytetrafluoroethylene, and obliquely placing a conductive glass substrate in the hydrothermal reaction kettle with the conductive side facing downwards;
s1.2: carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at 120 ℃ for 4 hours;
s1.3: after the reaction is finished, taking out the hydrothermal reaction kettle, naturally cooling the hydrothermal reaction kettle to room temperature, taking out a product in the hydrothermal reaction kettle, repeatedly washing the product to be neutral by using ethanol and deionized water, and drying the product in a forced air drying oven at 70 ℃ to constant weight;
s1.4: placing the dried product in a muffle furnace, and keeping the temperature of the muffle furnace at 600 ℃ for 1 hour in the air atmosphere to obtain Fe 2 O 3 (Ti) nano-arrays;
s2: placing the mixed solution obtained in the step S1 into a hydrothermal reaction kettle lined with polytetrafluoroethylene, and carrying out hydrothermal reaction on the hydrothermal reaction kettle in a forced air drying oven at the temperature of 100-120 ℃ for 16-20 hours;
s3: fully washing a product in the hydrothermal reaction kettle by using DMF (dimethyl formamide) and ethanol, and drying the product in a vacuum drying oven to constant weight to obtain Fe with a core-shell structure 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photocatalyst, NH 2 Average shell thickness of MIL-101 (Fe) 2.5-4nm.
2. Fe as claimed in claim 1 2 O 3 (Ti)@NH 2 A preparation method of-MIL-101 (Fe) composite photoelectric catalyst, which is characterized by comprising the following steps: fe in step S1 2 O 3 The (Ti) nanoarray is a rod-like structure, and the average diameter of the rod is 45-55nm.
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