CN109205553B - Modified mesoporous metal oxide nano-particles and preparation method and application thereof - Google Patents
Modified mesoporous metal oxide nano-particles and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a modified mesoporous metal oxide nanoparticle, which is prepared from mesoporous metal oxide and O on the surface of the mesoporous metal oxide2‑Covalently bonded halogen molecules, and the proportion of the mesoporous metal oxide to the halogen molecules is 100mg (0.01-0.1) mol, the mesoporous size of the mesoporous metal oxide is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-300 m-2/g。
Description
Technical Field
The invention belongs to the technical field of nanogold preparation, and particularly relates to a modified mesoporous metal oxide nanoparticle and a preparation method and application thereof.
Background
The solid nanometer material with nanometer scale has unique properties including adsorptivity, catalysis, mesoporous property and the like. In addition, some nanoparticles can exhibit certain bactericidal properties in different states (e.g., solid, slurry, microemulsion). Currently, there are two main types of nanocrystals with bactericidal properties: one class is metal nanoparticles such as silver particles, which, due to their size between macroscopic and microscopic atoms, macroscopic and microscopic molecules, can exhibit special effects such as surface effects, small size effects, quantum size effects and macroscopic quantum tunneling effects, which can allow the metal nanoparticles to easily enter the interior of pathogens. The nano silver particles are small in size, large in body surface area ratio, different in surface chemical bond state and electronic state from those in the nano crystal, and the surface activity is increased due to the defects of surface atoms, so that pathogenic microorganisms such as bacteria, fungi, mycoplasma and chlamydia can be killed, and basic conditions are provided for using the nano silver particles as antibacterial agents. In addition, the nano silver has strong penetrating power, can fully contact and attack pathogens, thereby exerting strong biological effect, has the advantages of high safety, wide antibacterial range, long lasting sterilization time and the like, and has far greater antibacterial property on bacilli, cocci and myceliums than the traditional silver ions. Another class of nanoparticles having an antibacterial effect is the use of mesoporous metal oxides such as: MgO, CeO, Al2O3And the like, which can effectively remove viruses. However, it is not limited toWhen the mesoporous metal oxide is used for preparing the heat-proof filter medium, only viruses can be removed but not killed, and the application range of the mesoporous metal oxide is relatively limited. At present, the virus filtering effect is mainly improved by changing the morphology and the particle size of the mesoporous oxide. In addition, the metal oxide nanoparticles can be used in optoelectronic devices as electron barrier materials. However, since the charge mobility of metal oxide nanoparticles such as zinc oxide nanoparticles varies little with the size of the particles, and the charge mobility of the charge transport layer required for different light emitting materials varies in size, there is a certain limit to the selection of the light emitting material when the metal oxide nanoparticles are used as the material for the electron blocking layer.
Disclosure of Invention
The invention aims to provide a modified mesoporous metal oxide nanoparticle, a preparation method and application thereof, and aims to solve the problem of limited application (such as virus filtration and virus killing failure, small change of charge mobility along with size and limited selection of luminescent materials) caused by insufficient performance of the mesoporous metal oxide nanoparticle before modification.
The invention is realized by the following steps that modified mesoporous metal oxide nanoparticles are prepared from mesoporous metal oxide and O on the surface of the mesoporous metal oxide2-Covalently bonded halogen molecules, and the proportion of the mesoporous metal oxide to the halogen molecules is 100mg (0.01-0.1) mol, the mesoporous size of the mesoporous metal oxide is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-300 m-2/g。
Correspondingly, the preparation method of the modified mesoporous metal oxide nanoparticle comprises the following steps:
dissolving a high molecular polymer in a polar organic solvent, adding a metal halide solution, adding a cation precursor of a target mesoporous metal oxide for reaction, centrifuging, drying and calcining to prepare the mesoporous metal oxide;
and placing the mesoporous metal oxide in a flowing halogen gas environment to obtain the modified mesoporous metal oxide nanoparticles.
And an application of the modified mesoporous metal oxide nanoparticles, in particular to a biological sterilization material using the modified mesoporous metal oxide nanoparticles.
An application of modified mesoporous metal oxide nanoparticles, in particular to an application of the modified mesoporous metal oxide nanoparticles as an electron transport layer material of an electric luminescent device.
The modified mesoporous metal oxide nano-particles, the halogen molecules and O on the surface of the mesoporous metal oxide provided by the invention2-Is covalently bound. On one hand, the oxidation performance of the mesoporous metal oxide is improved, and the modified mesoporous metal oxide nano particles have good sterilization effect. On the other hand, the mesoporous metal oxide can change the charge mobility of the metal oxide after adsorbing halogen molecules, and when the modified mesoporous metal oxide nanoparticles are used as an electron blocking layer of an electrical device such as an LED, the modified mesoporous metal oxide nanoparticles can be rapidly transmitted through a charge dipole effect, so that the charge transmission performance between interfaces (a transmission layer and a functional layer interface) is changed.
The preparation method of the modified mesoporous metal oxide nano-particles provided by the invention comprises the steps of firstly, reacting a metal halide solution with a metal cation precursor, and then calcining at high temperature to prepare the mesoporous metal oxide; and then introducing halogen gas to perform surface passivation on the mesoporous metal oxide with the mesh structure (the metal oxide with the mesh structure has stronger adsorption capacity due to the active corner position on the surface and can be combined with fluorine, chlorine, bromine and iodine), the method is simple and easy to control, and the obtained modified mesoporous metal oxide nanoparticles not only have good sterilization effect, but also can be used as an electronic barrier layer of optical devices such as LEDs, and the charge transmission performance between interfaces (a transmission layer and a functional layer interface) is improved.
When the modified mesoporous metal oxide nano particles are used as biological sterilization materials, the modified mesoporous metal oxide nano particles not only can filter bacteria, but also can effectively sterilize bacteria.
When the modified mesoporous metal oxide nanoparticles are used as an electron transport layer material of an electric light-emitting device, the charge transport performance between interfaces (a transport layer and a functional layer interface) can be improved.
Drawings
Fig. 1 is a schematic diagram of preparing modified mesoporous metal oxide nanoparticles according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides modified mesoporous metal oxide nanoparticles, which are prepared from mesoporous metal oxide and O on the surface of the mesoporous metal oxide2-Covalently bonded halogen molecule, the mesoporous size of the mesoporous metal oxide is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-300m2/g。
In the embodiment of the invention, the surface of the mesoporous metal oxide has defects such as O2-The surface of the mesoporous metal oxide has an uneven force field, and the surface atoms of the mesoporous metal oxide have certain bonding capability. When halogen gas molecules collide with the surface of the mesoporous metal oxide, the halogen molecules and O on the surface of the mesoporous metal oxide2-The shared electron cloud density forms an adsorption chemical bond.
Specifically, in the embodiment of the present invention, the mesoporous metal oxide is a mesoporous metal oxide having a mesh structure, the size of the mesopores of the mesoporous metal oxide is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-300m2(ii) in terms of/g. The mesoporous metal oxide has a plurality of active edges and angular positions (O) with stronger adsorption capacity due to larger specific surface area and higher pore channel structure2-) Thereby providing an effective site for binding of the halogen molecule.
In the embodiment of the invention, the mesoporous metal oxideThe proportion of the compound to the halogen molecule is 100mg (0.01-0.1) mol, on one hand, O on the surface of the mesoporous metal oxide can be ensured2-Is sufficiently effective to bind to the halogen molecule; on the other hand, since halogen donors such as halogen molecules and interhalogen compounds have strong oxidizing property, when the content is too large, the halogen donors can react with other groups on the surface of the mesoporous metal oxide, thereby affecting the performance of the modified mesoporous metal oxide nanoparticles. The proportion of the mesoporous metal oxide to the halogen molecules is 100mg (0.01-0.1) mol, and the embodiment of the invention modifies the mesoporous metal oxide by strictly controlling the proportion of the mesoporous metal oxide to the halogen molecules, so that the halogen-adsorbed mesoporous metal oxide nanocrystal not only has a sterilization effect, but also can be prepared into a charge blocking layer of an electrical device such as an LED, and the charge transmission performance between the transmission layer and the functional layer interface is improved.
In the embodiment of the present invention, the mesoporous metal oxide includes, but is not limited to, mesoporous alumina nanoparticles, mesoporous titania nanoparticles, mesoporous ceria nanoparticles, mesoporous magnesia nanoparticles, and mesoporous calcium oxide nanoparticles.
In the embodiment of the invention, the halogen molecules are elementary halogen molecules and/or interhalogen compound molecules, wherein the elementary halogen molecules are Cl2、Br2、I2、F2The interhalogen molecule comprises ICl, IBr, ICl3At least one of (1). The preferred halogen molecules include those having a strong oxidizing ability, which are effective in killing germs; meanwhile, after the preferable halogen molecules are adsorbed on the surface of the porous metal oxide, the charge mobility of the metal oxide can be effectively changed.
The modified mesoporous metal oxide nanoparticles, the halogen molecules and O on the surface of the mesoporous metal oxide provided by the embodiment of the invention2-And (4) covalently bonding. On one hand, the oxidation performance of the mesoporous metal oxide is improved, and the modified mesoporous metal oxide nano particles have good sterilization effect. On the other hand, after the mesoporous metal oxide adsorbs halogen molecules, the charge mobility of the metal oxide can be changedAnd the size of the modified mesoporous metal oxide nanoparticles is that when the modified mesoporous metal oxide nanoparticles are used as an electron blocking layer of an electrical device such as an LED, the modified mesoporous metal oxide nanoparticles can be rapidly transmitted through a charge dipole effect, so that the charge transmission performance between interfaces (a transmission layer and a functional layer interface) is changed.
The modified mesoporous metal oxide nanoparticles provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention also provides a preparation method of the modified mesoporous metal oxide nanoparticles, which comprises the following steps:
s01, dissolving a high molecular polymer in a polar organic solvent, adding a metal halide solution, adding a cation precursor of a target mesoporous metal oxide, reacting, centrifuging, drying and calcining to prepare the mesoporous metal oxide;
s02, placing the mesoporous metal oxide in a flowing halogen gas environment to obtain modified mesoporous metal oxide nanoparticles.
Specifically, in the step S01, a high molecular weight polymer is dissolved in the polar organic solvent, wherein the high molecular weight polymer includes a polyglycol, specifically, the polyglycol includes at least one of polyethylene glycol, polypropylene glycol and polybutylene glycol, but is not limited thereto. The polar organic solvent is an organic solvent capable of dissolving the high molecular polymer, and includes but is not limited to at least one of ethanol and methanol. And after magnetic stirring is carried out uniformly, dropwise adding a metal halide solution, wherein the metal halide solution is used as a catalyst to promote the decomposition of a cation precursor of the target mesoporous metal oxide to form the corresponding mesoporous metal oxide. Preferably, the metal halide solution includes at least one of a sodium chloride solution, a sodium bromide solution, a sodium fluoride solution, a sodium iodide solution, a calcium chloride solution, a calcium bromide solution, a calcium fluoride solution, and a calcium iodide solution. Particularly preferably, the concentration of the metal halide solution is 0.05-0.5mol/L, and if the concentration of the metal halide solution is too low, the effect of assisting in forming a sol-gel solution is not good; if the concentration of the metal halide solution is too high, the cation precursor is decomposed too quickly, which may hinder the formation of the mesoporous metal oxide.
Further, adding a cation precursor of a target mesoporous metal oxide, and stirring for reaction, wherein the mesoporous metal oxide is at least one of a titanium metal oxide, an aluminum metal oxide, a calcium metal oxide, a cerium metal oxide, and a magnesium metal oxide, and the cation precursor of the titanium metal oxide includes, but is not limited to, at least one of butyl titanate, propyl titanate, and ethyl titanate; the cationic precursor of the aluminum metal oxide includes but is not limited to at least one of butyl aluminate, ethyl aluminate, propyl aluminate solution; the cation precursor of the calcium metal oxide comprises at least one of but not limited to butyl calcium carbonate, ethyl calcium carbonate and propyl calcium carbonate; the cation precursor of the cerium metal oxide comprises at least one of cerium nitrate and cerium sulfate; the cation precursor of the magnesium metal oxide includes but is not limited to at least one of magnesium hydroxide and magnesium chloride.
In the embodiment of the invention, the added cation precursor is a cation precursor solution, and preferably, the concentration of the cation precursor solution of the mesoporous metal oxide is 0.05-0.2 mmol/L. If the concentration of the cationic precursor solution of the mesoporous metal oxide is too low, the reaction rate is too slow; if the concentration of the cationic precursor solution of the mesoporous metal oxide is too high, the formed mesoporous metal oxide particles are too large, and the specific surface area is reduced. And adding the cation precursor, and stirring for 5-30 hours. If the stirring time is too short, the yield of the mesoporous metal oxide is too low, and even the mesoporous metal oxide is difficult to form.
Further preferably, the amounts of the cationic precursor, the high molecular polymer and the metal halide solution are as follows: the ratio of the cation precursor, the high molecular polymer and the metal halide is (0.05-0.2) mmol, (20-80) ml, (0.01-0.2) mmol, so that the mesoporous size is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-2A mesoporous metal oxide per gram.
Because the reaction is exothermic, the mixed solution is cooled to room temperature after the reaction is finished, and the mesoporous metal oxide is prepared by drying after centrifugal separation and finally high-temperature calcination. Wherein the drying condition may be vacuum drying, and as a specific example, the drying condition is vacuum drying at 80 ℃ for 24 hours to obtain powder. In the embodiment of the invention, organic matters and other impurities in the obtained solid powder can be volatilized by high-temperature calcination to form mesopores. Preferably, the calcination temperature is 300-800 ℃ to ensure that the volatile organic compounds and other impurities are sufficiently removed, and the quality of the obtained mesoporous metal oxide is not affected.
In a specific embodiment, the step S01 includes: and (4) placing the mesoporous metal oxide prepared in the step (S01) in a two-way container, introducing halogen gas into one end of the two-way container, introducing the other end of the two-way container into a recovery device, and continuously introducing the halogen gas for 24-36 hours to prepare the modified mesoporous metal oxide nanoparticles.
In the step S02, the mesoporous metal oxide prepared in the step S01 is placed in a two-way container, and halogen gas is introduced into one end of the two-way container, and the other end of the two-way container is connected to a recovery device. By the reaction system, on one hand, the reaction efficiency of halogen gas and the metal oxide nanoparticles can be improved; on the other hand, the utilization rate of the halogen gas can be improved, and the influence of the leakage of the halogen gas on the surrounding environment can be prevented. In the embodiment of the invention, the halogen gas comprises a simple halogen substance and/or an interhalogen compound with stronger oxidizing ability and stronger electron-obtaining ability, wherein the simple halogen substance comprises Cl2、Br2、I2、F2The interhalogen compounds include ICl, IBr, ICl3. The mesoporous metal oxide has more oxygen vacancies (O)2-) Further, since the surface polarization charge is generated due to the high surface energy, the halogen compound or the interhalogen compound is easily adsorbed and bonded. Specifically, halogen and oxygen vacancy covalent ligand on the surface of the mesoporous metal oxide, such as M.X, wherein M is O2-(ii) a X is Cl2、Br2、I2、F2、ICl、IBr、ICl3And represents a shared electron. The preparation of the modified mesoporous metal oxide nanoparticle through the step S02 is schematically shown in the figure1 is shown.
Furthermore, the flow rate of the halogen gas can be adjusted according to the size of the reaction scale, for example, the halogen gas is introduced into the reaction system according to the amount of 0.001-0.1 mmol/min.
According to the preparation method of the modified mesoporous metal oxide nanoparticles provided by the embodiment of the invention, firstly, a mesoporous metal oxide is prepared by reacting a metal halide solution with a metal cation precursor and then calcining at high temperature; and then introducing halogen gas to perform surface passivation on the mesoporous metal oxide with the mesh structure (the metal oxide with the mesh structure has stronger adsorption capacity due to the active corner position on the surface and can be combined with fluorine, chlorine, bromine and iodine), the method is simple and easy to control, and the obtained modified mesoporous metal oxide nanoparticles not only have good sterilization effect, but also can be used as an electronic barrier layer of optical devices such as LEDs, and the charge transmission performance between interfaces (a transmission layer and a functional layer interface) is improved.
The embodiment of the invention also provides application of the modified mesoporous metal oxide nanoparticles, and particularly provides application of the modified mesoporous metal oxide nanoparticles as a biological sterilization material.
The embodiment of the invention provides application of modified mesoporous metal oxide nanoparticles, and particularly relates to application of the modified mesoporous metal oxide nanoparticles as an electron transport layer material of an electric light-emitting device. Wherein the electrical light emitter includes a QLED (Quantum dot light emitting diode) device and an OLED (organic light emitting diode) device.
When the modified mesoporous metal oxide nano particles are used as biological sterilization materials, the modified mesoporous metal oxide nano particles not only can filter bacteria, but also can effectively sterilize bacteria.
When the modified mesoporous metal oxide nanoparticles are used as an electron transport layer material of an electric light-emitting device, the charge transport performance between interfaces (a transport layer and a functional layer interface) can be improved.
The following description will be given with reference to specific examples.
Example 1
The halogen modified mesoporous titanium dioxide nano-particles are prepared by the following steps:
s11, preparing mesoporous titanium dioxide (TiO)2): dissolving 2.5g of polyethylene glycol (PEG) in 50ml of absolute ethyl alcohol, uniformly stirring by magnetic force, dropwise adding 0.5ml of sodium chloride solution with the concentration of 0.1mol/L, continuously stirring until the solution is uniformly mixed, slowly dropwise adding 1ml of butyl titanate with the concentration of 0.1mol/L, stopping stirring until white turbidity appears, standing at room temperature for 10h, performing vacuum drying at 80 ℃ for 24h through centrifugal separation to obtain white powder, and finally calcining at 500 ℃ for 2h to obtain a sample.
S12, preparing and adsorbing chlorine (Cl)2) Mesoporous titanium dioxide (TiO) of2)：
200mg of mesoporous titanium dioxide (TiO) is taken2) Placing in a double-pass glass tube, wherein one end of the double-pass glass tube is filled with chlorine gas according to the gas flow of 1-2ml/s, and the other end of the double-pass glass tube is inserted into water through a rubber tube; continuously ventilating for 24h to ensure that the mesoporous titanium dioxide (TiO)2) Can fully adsorb chlorine molecules.
Bacteria were killed using the halogen-modified mesoporous titania nanoparticles prepared in example 1, specifically, two petri dishes a and B containing the same number of bacteria (100) were taken, wherein a contained the halogen-modified mesoporous titania nanoparticles prepared in example 1, and B contained no. Both dishes were incubated under the same conditions for 24 h. After the end of the time, a quantitative sample was taken from each of the two petri dishes and then diluted with 5ml of physiological saline, 50. mu.l of the sample was taken out and dropped on a clean glass slide to observe the concentration of bacteria in the two petri dishes A and B under a microscope. The results showed that the concentration of bacteria in the dish A to which the halogen-modified mesoporous titania nanoparticles prepared in example 1 were added was about (1-10)/μm2The concentration of bacteria in the culture dish B without the halogen-modified mesoporous titanium dioxide nanoparticles was about (100-)/μm2The bacterial concentration of the halogen modified mesoporous titanium dioxide nano-particles prepared in the embodiment 1 of the invention is obviously higher. It can be seen that the halogen-modified mesoporous titania nanoparticles prepared in example 1 have a good sterilization effect.
Example 2
The halogen modified mesoporous titanium dioxide nano-particles are prepared by the following steps:
s21, preparing mesoporous titanium dioxide (TiO)2): dissolving 2.5g of polyethylene glycol (PEG) in 50ml of absolute ethyl alcohol, uniformly stirring by magnetic force, dropwise adding 0.5ml of sodium bromide solution with the concentration of 0.1mol/L, continuously stirring until the solution is uniformly mixed, slowly dropwise adding 1ml of butyl titanate with the concentration of 0.1mol/L, stopping stirring until white turbidity appears, standing at room temperature for 10h, performing vacuum drying at 80 ℃ for 24h through centrifugal separation to obtain white powder, and finally calcining at 500 ℃ for 2h to obtain a sample.
S22, preparing bromine gas (Br) adsorbed2) Mesoporous titanium dioxide (TiO) of2): 200mg of mesoporous titanium dioxide (TiO) is taken2) Placing in a double-pass glass tube, wherein one end of the double-pass glass tube is filled with chlorine gas according to the gas flow of 1-2ml/s, and the other end of the double-pass glass tube is inserted into water through a rubber tube; continuously ventilating for 24h to ensure that the mesoporous titanium dioxide (TiO)2) Can fully adsorb chlorine molecules.
The halogen-modified mesoporous titanium dioxide nanoparticles prepared in example 2 were used to prepare QLED devices, specifically,
depositing a hole injection layer, a hole transport layer, an electron barrier layer and a quantum dot light emitting layer on the cleaned ITO glass sheet in sequence, wherein the hole injection layer is made of PEDPOT (polymer injection moulding compositions) PSS (polyvinyl pyrrolidone), and the electron barrier layer is made of PVK (polyvinyl pyrrolidone);
in a glove box, the halogen modified mesoporous titanium dioxide nanoparticle solution prepared in example 2 is deposited on a quantum dot light emitting layer to prepare an electron transport layer;
and sequentially depositing TPBI and an aluminum electrode on the electron transport layer to prepare the QLED device.
Mesoporous titanium dioxide nanoparticles which are not modified by halogen are deposited on the quantum dot light emitting layer to prepare the electron transmission layer, and other parts are the same as the method for preparing the comparative QLED device.
The result shows that the charge mobility of the electron transport layer of the QLED device prepared by using the halogen-modified mesoporous titanium dioxide nanoparticles as the electron transport material is improved compared with the QLED device prepared by using the non-halogen-modified mesoporous titanium dioxide nanoparticles as the electron transport material.
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 present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The modified mesoporous metal oxide nanoparticle is characterized by comprising mesoporous metal oxide and O on the surface of the mesoporous metal oxide2-Halogen molecules which share electron clouds and are covalently combined, wherein the size of the mesopores of the mesoporous metal oxide is 1-10nm, and the specific surface area of the mesoporous metal oxide is 150-300m2/g。
2. The modified mesoporous metal oxide nanoparticle of claim 1, wherein the mesoporous metal oxide is a mesoporous alumina nanoparticle, a mesoporous titania nanoparticle, a mesoporous ceria nanoparticle, a mesoporous magnesia nanoparticle, a mesoporous calcia nanoparticle.
3. The modified mesoporous metal oxide nanoparticle according to claim 1 or 2, wherein the halogen molecule is an elemental halogen molecule and/or an interhalogen molecule, wherein the elemental halogen molecule is Cl2、Br2、I2、F2The interhalogen molecule comprises ICl, IBr, ICl3The ratio of the mesoporous metal oxide to the halogen molecule is 100mg (0.01-0.1) mol.
4. A method for preparing the modified mesoporous metal oxide nanoparticles according to any one of claims 1 to 3, comprising the following steps:
dissolving a high molecular polymer in a polar organic solvent, adding a metal halide solution, adding a cation precursor of a target mesoporous metal oxide for reaction, centrifuging, drying and calcining to prepare the mesoporous metal oxide;
and placing the mesoporous metal oxide in a flowing halogen gas environment to obtain the modified mesoporous metal oxide nanoparticles.
5. The method for preparing modified mesoporous metal oxide nanoparticles as claimed in claim 4, wherein the reaction time is 5-30 hours, and the calcination temperature is 300-800 ℃.
6. The method of preparing modified mesoporous metal oxide nanoparticles as claimed in claim 4, wherein the metal halide solution is at least one of a sodium chloride solution, a sodium bromide solution, a sodium fluoride solution, a sodium iodide solution, a calcium chloride solution, a calcium bromide solution, a calcium fluoride solution, a calcium iodide solution; and/or
The concentration of the metal halide solution is 0.05-0.5 mmol/ml.
7. The method of any one of claims 4-6, wherein the mesoporous metal oxide is one of a titanium metal oxide, an aluminum metal oxide, a calcium metal oxide, a cerium metal oxide, and a magnesium metal oxide, wherein the cationic precursor of the titanium metal oxide comprises at least one of butyl titanate, propyl titanate, and ethyl titanate; the cation precursor of the aluminum metal oxide comprises at least one of butyl aluminate, ethyl aluminate and propyl aluminate; the cation precursor of the calcium metal oxide comprises at least one of calcium butyl carbonate, calcium ethyl carbonate and calcium propyl carbonate; the cation precursor of the cerium metal oxide comprises at least one of cerium nitrate and cerium sulfate; the cation precursor of the magnesium metal oxide comprises at least one of magnesium hydroxide and magnesium chloride; and/or
The polar organic solvent is at least one of ethanol, methanol and acetone; and/or
The high molecular polymer comprises polyglycol, the polyglycol includes at least one in polyethylene glycol, polypropylene glycol, polytetramethylene glycol; and/or
The dosage of the cation precursor, the high molecular polymer and the metal halide solution meets the following requirements: the proportion of the cation precursor, the high molecular polymer and the metal halide is (0.05-0.2) mmol, (20-80) ml, (0.01-0.2) mmol.
8. The method of any one of claims 4-6, wherein the halogen gas is an elemental halogen and/or an interhalogen compound, wherein the elemental halogen comprises Cl2、Br2、I2、F2The interhalogen compounds include ICl, IBr, ICl3The mesoporous metal oxide is placed in a flowing halogen gas environment for 24-36 hours.
9. Use of modified mesoporous metal oxide nanoparticles according to any of claims 1 to 3 as a biological bactericidal material.
10. Use of modified mesoporous metal oxide nanoparticles according to any of claims 1 to 3 as an electron transport layer material for semiconductor light emitting devices.
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