CN107413387B - Preparation method of manganese-doped titanium dioxide nanofiber material - Google Patents
Preparation method of manganese-doped titanium dioxide nanofiber material Download PDFInfo
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- CN107413387B CN107413387B CN201710767439.0A CN201710767439A CN107413387B CN 107413387 B CN107413387 B CN 107413387B CN 201710767439 A CN201710767439 A CN 201710767439A CN 107413387 B CN107413387 B CN 107413387B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a preparation method of a manganese-doped titanium dioxide nanofiber material, belongs to the technical field of photocatalytic materials, and has high photocatalytic degradation efficiency on organic pollutants in the environment. The preparation method comprises the following steps: dispersing amphiphilic cationic short peptide in water, performing ultrasonic dispersion, adjusting the pH value of the solution, and standing at room temperature for more than one week to obtain a short peptide self-assembly solution; sequentially adding a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution into the amphiphilic short peptide self-assembly solution, uniformly mixing by vortex, reacting at room temperature, and centrifuging to obtain a grey brown precipitate; and washing the grey brown precipitate, heating, and removing the short peptide template to obtain the manganese-doped titanium dioxide nanofiber material. The method can be used for preparing the manganese-doped titanium dioxide nanofiber material.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of a manganese-doped titanium dioxide nanofiber material.
Background
The titanium dioxide has the characteristics of no toxicity, low price, high activity, ultraviolet radiation resistance, strong oxidant resistance, acid and alkali resistance and the like, is an attractive multifunctional semiconductor material, and has huge application prospect in the fields of photonic devices, solar cells, photocatalysis and the like. However, the inherent forbidden band width of titanium oxide is too wide (the forbidden band width of anatase is 3.0eV, and the forbidden band width of rutile is 3.2eV), so that the titanium oxide can only be excited by ultraviolet light with the wavelength of less than 387nm (the ratio of the forbidden band width to the forbidden band width of rutile is less than 5 percent in sunlight), and is not sensitive to visible light with the ratio of more than 50 percent. Too low light utilization severely limits the utility of titanium oxide. Therefore, researchers have conducted a great deal of research work to adjust the forbidden band width of titanium oxide and to expand the photoresponse range thereof toward the visible region. Currently, the major modification techniques for titanium oxide photocatalysts at home and abroad include ion doping (see Mao Y. et al, German applied chemistry 2014, 53:10485), surface noble metal deposition (Yun J. et al, American society for chemistry applied materials at the interface 2015, 7:2055), semiconductor compounding (Thapa A. et al, nanometer research 2014, 7:1154), and photosensitization of metal complexes and dyes (Altin I. et al, desalination and water treatment 2016, 57: 16196). Among them, doping other elements into the titanium oxide phase to expand the absorption boundary toward the visible region is considered to be an efficient and simple method, and has received attention from many researchers.
Doping modifications of titanium oxide include non-metal ion doping (e.g., carbon, nitrogen, sulfur, fluorine, etc.) and metal ion doping (e.g., iron, cobalt, copper, vanadium, gallium, etc.). The non-metal ions are generally present as anions in the main phase, while the metal ions are present as cations in the titanium oxide. Compared with non-metal doping, which requires complex process control (such as anion doping through a flame reaction), transition metal cation doping is simpler and is considered to be a promising doping means. Among many transition metal elements, polyvalent metals such as manganese and iron have been proved to enhance the absorption of visible light by titanium oxide, and after manganese ions are doped into rutile titanium oxide, a curved intermediate energy band is introduced into a contracted forbidden band gap, which can constitute a significant change of an electron energy band structure. This curved Intermediate Band (IB) will act as a "stepping stone" to effectively participate in the electron transfer of the valence band during light absorption at different wavelengths, resulting in a significant red-shift in the light absorption of the material.
As a photocatalytic material, photocatalytic performance is controlled by its separation and transport properties of photogenerated electrons and holes, in addition to its light absorption capability. The one-dimensional nano material has a certain quantum size effect, and can improve the quantum yield of the photocatalytic reaction; in terms of optical properties, the one-dimensional nano material has a larger aspect ratio, and can remarkably enhance the scattering and absorption of light; in the microstructure, the one-dimensional nano material has a smaller electron migration path, which is beneficial to the transmission of electrons and delays the covering and extinguishing of the electrons. Therefore, the manganese-doped titanium dioxide nanofiber material with a controllable structure is expected to obtain higher sunlight utilization efficiency and photocatalytic conversion effect, and is applied to the fields of organic pollutant treatment, photoelectric/photochemical conversion and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a manganese-doped titanium dioxide nanofiber material, which can improve the sunlight utilization rate and the photocatalytic efficiency of titanium dioxide, so that the photocatalytic conversion efficiency and the degradation effect of organic pollutants are improved.
The invention provides a preparation method of a manganese-doped titanium dioxide nanofiber material, which comprises the following steps:
ultrasonically dispersing amphiphilic cationic short peptide molecules into water, adjusting the pH value of the solution, and placing the solution at room temperature for more than 1 week to obtain a self-assembly solution of the amphiphilic short peptide;
sequentially adding a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution into the amphiphilic short peptide self-assembly solution, uniformly mixing by vortex, reacting at room temperature for 10-24 hours, centrifuging to obtain a grey brown precipitate, washing the precipitate, heating at the temperature of 300 ℃ and 500 ℃ for 2-10 hours to remove a short peptide template to obtain a manganese-doped titanium dioxide nanofiber material;
the hydrophobic unit of the amphiphilic cationic short peptide molecule consists of 3-6 leucine, isoleucine, glycine and valine, the hydrophilic head group consists of 1-2 lysine, histidine and arginine, and a nanofiber structure can be formed in an aqueous solution.
Optionally, the titanium dioxide precursor is selected from at least one of n-butyl titanate, isopropyl titanate and bis (2-hydroxypropionic acid) diammonium bihydroxide titanium.
Preferably, the concentration of the amphiphilic short peptide is 0.5-10mmol L-1The concentration of the titanium dioxide precursor is 1-10mmol L-1The concentration of potassium permanganate is 0.001-0.1mmol L-1The concentration of the manganese nitrate is 0.0015-0.15mmol L-1。
Preferably, after the amphiphilic short peptide is ultrasonically dispersed in water, the pH value of the solution is adjusted to be in the range of 5-9.
Optionally, the washing treatment specifically includes washing the grayish brown precipitate with pure water and ethanol alternately.
Preferably, the rotation speed of the centrifugal treatment is 5000-.
Another aspect of the present invention provides a manganese-doped titanium dioxide nanofiber material prepared by the method according to any one of the above technical solutions.
In another aspect, the invention provides an application of the manganese-doped titanium dioxide nanofiber material in photocatalytic degradation of organic pollutants.
Compared with the prior art, the method induces the nucleation and growth of titanium dioxide on the surface of the template through the molecular recognition and the catalytic action of the organic template in the presence of the amphiphilic short peptide self-assembled nanofiber, and simultaneously introduces manganese ions into the titanium dioxide through the redox reaction of potassium permanganate and manganese nitrate regulated and controlled by the peptide template, thereby finally forming the manganese-doped titanium dioxide nanofiber material. Because of the doping guided by molecular recognition, the method has obvious advantages in the doping sites, the doping structure and the composition of the material. The manganese-doped titanium dioxide nanofiber material prepared by the method has the energy gap width of 1.55eV, and the absorption in a visible light region is obviously enhanced. Meanwhile, the doping of manganese ions and the existence of the one-dimensional nanostructure greatly improve the separation and transmission efficiency of current carriers, and the photoelectric conversion and transmission efficiency of the current carriers are greatly improved. A degradation experiment on model organic pollutants shows that compared with a commercialized nano titanium dioxide photocatalyst P25, the manganese-doped titanium dioxide nanofiber material prepared by the method has the advantages that the photocatalytic performance is obviously improved, the reduction of catalytic sites and the reduction of catalytic efficiency caused by aggregation are avoided, and the recycling stability is greatly improved. The manganese-doped titanium dioxide nanofiber material is prepared by the method under the conditions of room temperature and nearly neutral aqueous solution, and the whole synthesis process has the advantages of simplicity, energy conservation and environmental protection.
Drawings
FIG. 1 is a TEM photograph of a Mn-doped TiO nanofiber material prepared according to an embodiment of the present invention;
FIG. 2 shows UV-VIS absorption spectra of Mn-doped and pure titania nanofiber materials prepared according to an embodiment of the present invention;
FIG. 3A is a Ti 2p X ray photoelectron spectrum of manganese doped titanium dioxide nanofiber material and pure titanium dioxide nanofiber material prepared by the embodiment of the present invention;
FIG. 3B is a Mn2p X ray photoelectron spectrum of a manganese-doped titanium dioxide nanofiber material prepared according to an embodiment of the present invention;
FIG. 4 is a photo current response curve of the manganese-doped titanium dioxide nanofiber material and the pure titanium dioxide nanofiber material prepared in the embodiment of the present invention;
FIG. 5A is a graph showing photocatalytic methylene blue degradation curves of manganese-doped titanium dioxide nanofiber materials and commercial titanium dioxide nanomaterials prepared according to an embodiment of the present invention;
FIG. 5B is a graph showing the photocatalytic rhodamine B degradation curve of the manganese-doped titanium dioxide nanofiber material and the commercial titanium dioxide nanofiber material prepared in the embodiment of the present invention;
FIG. 6A is a concentration-reaction time curve of the manganese-doped titanium dioxide nanofiber material for cyclic photocatalytic degradation of methylene blue;
fig. 6B is a concentration-reaction time curve for cyclic photocatalytic degradation of methylene blue by commercial titanium dioxide (P25).
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of a manganese-doped titanium dioxide nanofiber material, which comprises the following steps:
s1: ultrasonically dispersing amphiphilic cationic short peptide molecules in water, adjusting the pH value of the solution, placing at room temperature for more than 1 week to obtain a self-assembled template of the amphiphilic cationic short peptide
In the step, the amphiphilic cationic short peptide is used for self-assembling to construct a one-dimensional organic template. Specifically, after the amphiphilic cationic short peptide is ultrasonically dispersed in water, the pH value of the system is adjusted to be nearly neutral, and the system is placed statically for more than one week to obtain the self-assembly solution of the amphiphilic short peptide. In the step, because the amphiphilic cationic short peptide is adopted, the near neutral pH value can protonate the side chain of the cationic amino acid residue, provide electrostatic action and stabilize the formed self-assembled structure, and the near neutral pH environment is favorable for obtaining a proper titanium dioxide generation rate.
S2: sequentially adding a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution into the amphiphilic short peptide self-assembly solution, uniformly mixing by vortex, reacting at room temperature for 10-24 hours, centrifuging to obtain a gray brown precipitate, washing the precipitate, heating at the temperature of 300-500 ℃ for 2-10 hours to remove the short peptide template, and obtaining the manganese-doped titanium dioxide nanofiber material.
In the step, in order to obtain the manganese-doped titanium dioxide nanofiber material, a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution are sequentially added into an amphiphilic short peptide assembly solution, so that the generation of titanium dioxide and the redox reaction of potassium permanganate and manganese nitrate are performed under the regulation and control of an amphiphilic short peptide self-assembly template. It is understood that the reaction time depends on the reaction sufficiency, and may be varied from 10, 12, 14, 16, 18, 20, 22, 24 hours or any other point within the above range. The precipitate formed was washed to remove the incompletely reacted titanium dioxide precursor, potassium permanganate and manganese nitrate. The heating is to remove the short peptide template and form a corresponding crystal structure, the heating temperature and the heating time are interdependent, and a person skilled in the art can adjust the temperature within the above range, and the heating temperature is high, and the heating time is short, but the heating temperature is too high, so that the structure and the morphology of the material are changed, and the heating temperature is too low to achieve the purpose of removing the short peptide template.
In one embodiment of the invention, the hydrophobic unit of the amphiphilic cationic short peptide consists of 3-6 leucine, isoleucine, glycine and valine, the hydrophilic head group consists of 1-2 lysine, histidine and arginine, and a nanofiber structure can be formed in an aqueous solution. In the embodiment, the amphiphilic cationic short peptide is composed of hydrophilic amino acid residues and hydrophobic amino acid residues, the type, the number and the position of the amino acid determine the form of the short peptide self-assembly, namely the shape and the structure of the template, and the structure and the property of the formed manganese-doped titanium dioxide nanofiber material are also greatly influenced. The hydrophilic head group on the surface of the short peptide template has important catalytic action on the formation of titanium dioxide besides attracting inorganic precursors with opposite charges to gather nearby the inorganic precursors, and plays an important guiding role on the structural rearrangement of manganese ions and titanium dioxide in the nanofiber material.
In an embodiment of the present invention, the titanium dioxide precursor is selected from at least one of n-butyl titanate, isopropyl titanate, and bis (2-hydroxypropionic acid) diammonium titanium dihydroxide. In this embodiment, because the hydrolysis rates of the titanium dioxide precursors are different, the generation rate of the titanium dioxide can be adjusted by selecting different precursors, so as to obtain a reaction system with a suitable nucleation rate and growth rate, so as to prepare the manganese-doped titanium dioxide nanofiber material with a designed structure.
In one embodiment of the invention, the concentration of the amphiphilic short peptide is 0.5-10mmol L-1The concentration of the titanium dioxide precursor is 1-10mmol L-1The concentration of potassium permanganate is 0.001-0.1mmol L-1The concentration of the manganese nitrate is 0.0015-0.15mmol L-1. In this embodiment, in order to obtain the manganese-doped titanium dioxide nanofiber material with higher light absorption efficiency and capability of photocatalytic degradation of organic matters, the generation rate of titanium dioxide and manganese ions (mainly Mn) need to be controlled4+And Mn3 +) The doping rate, the concentration of the titanium dioxide precursor and the manganese-containing compound (potassium permanganate solution and manganese nitrate solution) must be controlled within the above-mentioned ratio range, and it will be understood by those skilled in the art that the titanium dioxide concentration must be controlled within the above-mentioned concentration rangeThe solution prepared from the precursor, potassium permanganate and manganese nitrate can meet the requirement of the subsequent preparation of the manganese-doped titanium dioxide nanofiber material meeting the requirement, and therefore, the concentration of the titanium dioxide precursor is 1, 2, 4, 6, 8 or 10mmol L, and the adjustment can be carried out in the range according to the requirement-1And the like, or any value satisfying the above conditions. Similarly, the concentrations of potassium permanganate and manganese nitrate respectively satisfy 0.001-0.1mmol L-1、0.0015-0.15mmol L-1Any value of (a). In this embodiment, the amphiphilic short peptide mainly provides a template for preparing the manganese-doped titanium dioxide nanofiber material, and provides a catalytic effect for the hydrolytic polycondensation reaction of titanium dioxide in addition to providing a template guiding effect. Therefore, the concentration of the amphiphilic short peptide is related to whether the amphiphilic short peptide can form a stable one-dimensional assembly or not, and the reaction rate of the titanium dioxide is influenced. It can be understood that the amphiphilic short peptide in the concentration range can meet the requirement of preparing the manganese-doped titanium dioxide nanofiber material, and can be selected by a person skilled in the art according to the requirement.
In one embodiment of the invention, after dispersing the amphiphilic cationic short peptide in water, the pH is adjusted to a value in the range of 5 to 9. In the embodiment, the pH value is adjusted to be within the range of 5-9, so that the reaction system can be ensured to react in a near-neutral environment, and the whole synthesis process is ensured to have the characteristic of environmental friendliness. It is understood that the pH may be adjusted to 6, 7, 8, etc. or any other value within the above range.
In this step, the grayish brown precipitate is washed with pure water and ethanol in order to remove unreacted titanium dioxide precursor, potassium permanganate, manganese nitrate, and other compounds.
In an embodiment of the present invention, the rotation speed of the centrifugation process is 5000-. In the present embodiment, in order to separate the manganese-doped titanium dioxide nanofiber material, the manganese-doped titanium dioxide nanofiber material is separated by centrifugation. It is understood that when the rotation speed and time of the centrifugal treatment are limited to the above ranges, the separation effect of the nanomaterial may be better, and those skilled in the art may adjust the rotation speed and time within the above ranges according to actual situations. Specifically, the rotational speed of the centrifugal treatment may be 4000, 5000, 6000, 7000, 8000, 9000, 10000rpm, and the time may be 20, 30, 40, 50, 60 minutes, or the like, and any value may be used as long as the rotational speed and the time of the centrifugal treatment are within the above ranges.
Another embodiment of the present invention provides a manganese-doped titanium dioxide nanofiber material prepared by the method for preparing a manganese-doped titanium dioxide nanofiber material as described in any one of the above embodiments. The manganese-doped titanium dioxide nanofiber material prepared by the embodiment of the invention has manganese element mainly comprising Mn3+And Mn4+In the form of ions present in the titanium dioxide and substituting part of the Ti4+The ions enter the lattice structure of titanium dioxide, causing lattice contraction. The multi-valence manganese ion doping provides a plurality of intermediate energy levels for titanium dioxide, widens the photoresponse range of the material, enhances the visible light absorption capacity of the doped titanium dioxide, and can effectively inhibit the recombination of photo-generated electrons and holes by doping, so that the doped titanium dioxide has good photocatalytic degradation property for organic pollutants. On the other hand, the diameter of the manganese-doped titanium dioxide nanofiber material prepared by the embodiment of the invention is between 10 and 20 nanometers, the manganese-doped titanium dioxide nanofiber material has a large specific surface area and a large surface binding site, and the small electron migration path reduces the probability of recombination of photo-generated electrons and holes, so that the photocatalytic degradation efficiency of the material is further improved.
The manganese-doped titanium dioxide nanofiber material prepared by the embodiment of the invention has high specific surface area, good visible light response property and photoelectric transmission behavior, and thus has good photocatalytic property. When the photocatalyst is used for degrading organic pollutants, the photocatalyst has more excellent photocatalytic activity than commercial nano titanium dioxide, and has good reusability, so that the photocatalyst is suitable for being used as a photocatalytic reagent for organic pollutants in the environment.
In order to more clearly describe the preparation method of the manganese-doped titanium dioxide nanofiber material provided by the embodiment of the invention in detail, the following description is given with reference to specific embodiments.
Example 1
Preparation of manganese-doped titanium dioxide nanofiber material
(1) Preparation of amphiphilic cationic short peptide self-assembly solution
Dispersing a certain mass of amphiphilic cationic short peptide in water, performing ultrasonic dispersion, adjusting the pH value of the solution to 5-9, and standing at room temperature for 7-14 days to obtain an amphiphilic cationic short peptide self-assembly solution;
(2) synthesis of manganese-doped titanium dioxide nanofiber material
A) Sequentially adding a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution into the amphiphilic short peptide self-assembly solution, wherein the concentrations of the amphiphilic cation short peptide, the titanium dioxide precursor, the potassium permanganate and the manganese nitrate in the solution are respectively 0.5-10mmol L-1、1-10mmol L-1、0.001-0.1mmol L-1、0.0015-0.15mmol L-1Vortex and mix evenly, after reacting for 10-24 hours at room temperature, centrifugate (5000-;
B) washing the obtained grey brown precipitate by using pure water and ethanol alternately, and then heating the washed grey brown precipitate for 2 to 10 hours at the temperature of 300-.
Example 2
Appearance and structure characterization of manganese-doped titanium dioxide nanofiber material
Adopting a high-resolution transmission electron microscope, the model is as follows: JEM-2100UHR, Instrument manufacturer: japanese Electron (JEOL), acceleration voltage: 200 kV.
The embodiment combines a high-resolution transmission electron microscope to observe the morphology and the structure of the manganese-doped titanium dioxide nanofiber material, specifically, a sample is dispersed in ethanol and dropped on a copper net plated with a carbon film, the sample is placed in a sample chamber by using a special sample rod after being dried, the sample chamber is vacuumized, the proper resolution and the proper focal length are adjusted, the proper exposure time is selected, and an image is shot.
As a result, the obtained sample was found to have one-dimensional nanostructures with a diameter of 10 to 20nm and a length of several hundred nm or even several micrometers, as shown in fig. 1. And the random deposition is less outside the nano-fiber, which shows that the amphiphilic cation short peptide template has a better template guiding effect on inorganic minerals and precursors thereof, and the hydrolytic polycondensation of titanium dioxide and the redox reaction of potassium permanganate and manganese nitrate are carried out under the control of an organic template.
Example 3
Light response property characterization of manganese-doped titanium dioxide nanofiber material
An ultraviolet-visible spectrophotometer (attached diffuse reflectance measuring device-integrating sphere, manufactured by Shimadzu corporation, UV-1700PharmaSpec) is adopted, the scanning speed is medium speed, the slit width is 1nm, the measurement range is 200-800nm, and the sample is coated on a barium sulfate sheet and tableted for measurement by taking ultrafine barium sulfate as a reference.
As shown in FIG. 2, the light absorption of pure titanium dioxide is totally in the ultraviolet region, and basically no absorption exists in the visible region larger than 400nm, but the response of the material in the visible region is obviously enhanced after the modification by manganese doping, the forbidden band width of the material can reach 1.55eV according to the Kubelak-Munk formula, and the material can be adjusted by the change of the doping content and the doping mode.
Example 4
Analysis of composition and chemical state of manganese-doped titanium dioxide nanofiber material
The method comprises the following steps of uniformly spreading a powder sample on an aluminum foil, covering the aluminum foil with a sheet of aluminum foil, flattening the aluminum foil by using a hydraulic press, uncovering the aluminum foil, adhering the pressed sheet sample on a sample support by using a conductive adhesive tape, placing the sample support in an instrument sample chamber, vacuumizing the instrument sample chamber for 10 hours, and detecting.
As can be seen from FIG. 3A, the Ti 2p in the pure titanium dioxide sample1/2And Ti 2p3/2Has peak positions of 459.2eV and 464.9eV, respectively, and has a spin energy interval of5.7eV, corresponding to TiO2Ti of (A)4+And the ion is matched with the standard titanium dioxide spinning energy interval. After manganese is doped, the Ti 2p characteristic peak binding energy peak position moves towards the direction of low binding energy, but the spin energy interval is not changed, which shows that the Ti element in the titanium dioxide still uses Ti4+Are present. And (3) performing deconvolution peak processing analysis on the characteristic peak spectrogram of Mn2p in order to solve the valence state of the manganese element in the system. FIG. 3B is a Mn2p peak deconvolution spectrum of a manganese-doped titanium dioxide sample, and Mn2p can be seen by peak separation3/2The peak can be divided into two peaks, the peak positions respectively fall into 641.9eV and 643.1eV, and the two peaks respectively correspond to Mn3+And Mn4+Mn2p of3/2Peak by Mn3+/Mn4+The relative content of the manganese ions in different valence states can be calculated. Mn4+The binding energy of the ions is increased by 0.7eV compared with manganese dioxide, which is caused by the presence of Ti in the main phase4+And O2-Caused by the occurrence of chemical interactions. The results show that in the manganese-doped titanium dioxide nanofiber material system, the manganese element is Mn3+Ions and Mn4+Ion exists in two forms, and replaces part of Ti4+The doped titanium dioxide enters titanium dioxide crystal lattices, and shows that the system has a plurality of doping energy levels, which is more beneficial to widening the photoresponse range of the titanium dioxide.
Example 5
Photoelectric response property characterization of manganese-doped titanium dioxide nanofiber material
The test was performed using an electrochemical workstation (Shanghai Chenghua instruments Co., Ltd., CHI 660D). A three-electrode system is adopted, the prepared sample is taken as a working electrode, and the working area is 1cm2. The counter electrode is a platinum sheet electrode, the reference electrode is a saturated dry mercury electrode (SCE), and the electrolyte is 1Mol L-1Na of (2)2SO4And (3) solution. A300W xenon lamp is used as a light source, and a filter is added when the xenon lamp is used, wherein the wavelength range is more than 420 nm. The preparation process of the working electrode comprises the following steps: 0.2g of the sample was mixed with 0.06g of polyethylene glycol (PEG, molecular weight 4000), and 1mL of ethanol was added thereto, followed by sufficient stirring and grinding to prepare a slurry. A blank area of 1cm multiplied by 1cm is stuck on the conductive glass (ITO) by transparent adhesive,and coating the prepared slurry on the area, drying the coating at room temperature, and calcining the prepared electrode in a muffle furnace at 400 ℃ for 30 min.
Firstly, an open-circuit potential-time mode is used for testing the open-circuit potential of a sample under a light-proof condition, the surface charge distribution is different due to the difference of the conditions such as the appearance, the components and the like of the sample, the testing time of the open-circuit potential is not fixed, when the change of the open-circuit potential is less than 0.0001V within 30s in an experiment, the system is considered to reach a stable state, and the open-circuit potential value at the moment is recorded. And applying voltage with the magnitude of open-circuit potential to the working electrode, preventing the interference of the potential of the sample on photocurrent, ensuring that the current generated after the lamp is turned on is completely caused by illumination, and recording the change of the current along with time. During testing, the light source is switched on after 100s of stabilization, the lamps are sequentially switched on and off by taking 30s as a time interval, the cycle is repeated for 5 times, and the curve of the current changing along with the switching of the light source is recorded.
As can be seen from fig. 4, a strong current signal is detected at the instant of turning on the lamp, which indicates that a large amount of photoelectrons are generated by exciting the sample, and the photocurrent shows a decreasing trend with the increase of the illumination time, but the amplitude is not large. This is because during illumination, the photo-generated electrons and holes are in continuous rapid recombination, and the recombination rate is slightly faster than the rate at which the sample is excited by illumination to generate new photo-generated electrons, thus showing a decreased state of photocurrent in a macroscopic view. The faster the recombination rate, the steeper the current profile and the shorter the time to reach equilibrium. And after the lamp is turned on for 30s, the lamp is turned off to avoid light, and as the photoproduction electrons and the holes are quickly compounded, no new photoproduction electrons are generated any more, the photocurrent is almost instantaneously reduced to zero. And after the light is shielded for 30s, the lamp is turned on again for illumination, the sample is excited by light to generate a large amount of photoelectrons, and the photocurrent is increased rapidly. The comparison shows that the photocurrent intensity of the pure titanium dioxide sample is lowest during the lamp-on period, and the photocurrent intensity is rapidly increased after the manganese ions are doped, which can reach more than 4 times of that of the undoped sample. This is because the doping of the metal ions can act as shallow trap for electrons (or holes), thereby reducing the efficiency of the recombination of photo-generated electrons-holes.
Example 6
Characterization of properties of photocatalytic degradation organic pollutants of manganese-doped titanium dioxide nanofiber material
An ultraviolet-visible spectrophotometer (UV-1700 PharmaSpec, manufactured by Shimadzu corporation) was used, the slit width was 1nm, and the scanning range was 200-800 nm. Placing the sample under a xenon lamp, irradiating by adopting visible light with the wavelength of more than 420nm, and taking samples with different irradiation time for testing.
Fig. 5A is a Methylene Blue (MB) catalytic degradation experiment of manganese doped titanium dioxide samples and commercial titanium dioxide (P25) under visible light (>420 nm). MB reaches a maximum absorbance at 663nm, and a decrease in absorbance of the dye with time of illumination indicates that the dye is decomposed. In a blank experiment without adding a catalyst, the MB absorbance is slightly reduced under the irradiation of visible light, which shows that the aqueous solution of the MB absorbance is relatively stable under the visible light, the self-decomposition rate is slow, and the experimental result is not influenced. Manganese ion doped titanium dioxide has better photocatalytic efficiency than commercial nano titanium dioxide (P25). Fig. 5B shows a manganese-doped titanium dioxide sample and a rhodamine B (rhb) catalytic degradation experiment of commercial titanium dioxide (P25) under visible light (>420nm), and similar to MB degradation, the manganese-doped titanium dioxide nanofiber material shows a more excellent photocatalytic degradation effect.
The cycle stability of the photocatalyst is another very important evaluation criterion in addition to the photocatalytic activity. The recycling stability of the manganese-doped titanium dioxide nanofiber material was examined with reference to the commercialized nano titanium dioxide (P25), as shown in fig. 6A. After 5 times of circulation, the photocatalytic efficiency of the manganese-doped titanium dioxide nanofiber material is not obviously reduced, and the degradation rate of methylene blue can still be kept above 93%. After 5 cycles of experiments on P25, the degradation rate of methylene blue is reduced from 76% to 59%, as shown in FIG. 6B, which indicates that the manganese-doped titanium dioxide nanofiber material has better cycling stability than P25. The two materials show obvious difference in cycling stability, and the main reason is the difference of the morphological structures of the materials. The titanium dioxide photocatalytic degradation of organic matters mainly occurs on the surface of the material, the P25 is in the shape of nanoparticles, and the nanoparticles are easy to aggregate in the photocatalytic process, so that the specific surface area is reduced; the manganese-doped titanium dioxide nanofiber material synthesized by utilizing the amphiphilic cation short peptide has a one-dimensional structure, so that the migration path of electrons can be effectively shortened, the transmission efficiency of photon-generated carriers is improved, the photocatalytic activity of the material is enhanced, meanwhile, the aggregation phenomenon generated in the circulation process can be avoided, and the circulation stability of the material is further improved.
Claims (5)
1. A preparation method of a manganese-doped titanium dioxide nanofiber material is characterized by comprising the following steps:
ultrasonically dispersing amphiphilic cationic short peptide molecules into water, adjusting the pH value of the solution to be within the range of 5-9, and placing at room temperature for more than 1 week to obtain a self-assembly solution of the amphiphilic short peptide;
sequentially adding a titanium dioxide precursor, a potassium permanganate solution and a manganese nitrate solution into the amphiphilic short peptide self-assembly solution, uniformly mixing by vortex, reacting at room temperature for 10-24 hours, centrifuging to obtain a grey brown precipitate, washing the precipitate, heating at the temperature of 300 ℃ and 500 ℃ for 2-10 hours to remove a short peptide template to obtain a manganese-doped titanium dioxide nanofiber material;
the hydrophobic unit of the amphiphilic cationic short peptide consists of 3-6 leucine, isoleucine, glycine and valine, the hydrophilic head group consists of 1-2 lysine, histidine and arginine, and a nanofiber structure can be formed in an aqueous solution;
the titanium dioxide precursor is selected from at least one of n-butyl titanate, isopropyl titanate and bis (2-hydroxypropionic acid) diammonium dihydroxide titanium;
the concentration of the amphiphilic short peptide is 0.5-10 mmol.L-1The concentration of the titanium dioxide precursor is 1-10 mmol.L-1, the concentration of potassium permanganate is 0.001-0.1 mmol.L-1The concentration of manganese nitrate is 0.0015-0.15 mmol.L-1。
2. The method according to claim 1, wherein the washing treatment comprises washing the grayish brown precipitate with pure water and ethanol alternately.
3. The method as claimed in claim 1, wherein the rotation speed of the centrifugation treatment is 5000-10000rpm for 20-60 minutes.
4. A manganese-doped titanium dioxide nanofiber material prepared by the method for preparing a manganese-doped titanium dioxide nanofiber material as claimed in any one of claims 1 to 3.
5. Use of the manganese-doped titanium dioxide nanofiber material of claim 4 in photocatalytic degradation of organic pollutants.
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