CN109183124B - Narrow-forbidden-band black zirconia nanotube film and preparation method thereof - Google Patents
Narrow-forbidden-band black zirconia nanotube film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a narrow-forbidden-band black zirconia nanotube film and a preparation method thereof, wherein the optical forbidden band width of the black zirconia nanotube film is 1.0-3.0 eV. The preparation method comprises the following steps: (1) taking an inert electrode as a cathode and a polished zirconium sheet as an anode, and carrying out anodic oxidation in fluorine-containing electrolyte to prepare a zirconium oxide nanotube film; (2) and cleaning the zirconia nanotube film, drying, and performing heat treatment under the conditions of a protective or vacuum atmosphere and 800 ℃ to obtain the narrow-bandgap black zirconia nanotube film. The invention obtains the black zirconia nanotube film with narrow forbidden band width and simple preparation method at lower temperature, has lower cost and is suitable for large-scale production.
Description
Technical Field
The invention relates to a narrow-forbidden-band black zirconia nanotube film and a preparation method thereof.
Background
The problem of energy shortage is increasingly prominent, so that new energy materials become hot spots for research of all countries, and solar energy is undoubtedly the research focus of new energy by virtue of reproducibility; meanwhile, with the rapid development of chemical industry, pharmaceutical industry and other industries, the solution of environmental problems is also in urgent need of breakthrough, and the efficient pollution-free photocatalytic technology is concerned. However, the fundamental reason for limiting the application of solar energy or photocatalytic technology is that the existing materials have various problems such that the utilization rate of sunlight is not high. The light absorption capability mainly depends on the energy band structure and the surface state of the material, and the light absorption is usually facilitated by reducing the forbidden band width of the material and increasing the surface activity and the specific surface area of the material. The titanium oxide material is the most studied material applied to the photocatalysis direction in recent years, the forbidden band width of the titanium oxide material is about 3.2eV, the titanium oxide material can only absorb ultraviolet light, and the absorption capacity of the titanium oxide in the visible light region is greatly improved by means of titanium oxide surface modification, doping and the like. However, the titanium oxide has a positive conduction band position due to its energy band structure, which limits its application in photodegradation of organic pollutants and photoreduction. Zirconium oxide is used as a wide bandgap semiconductor with stable physicochemical properties, the position of a conduction band is more negative than that of titanium oxide, and the zirconium oxide has great potential in the fields of photodegradation, photoreduction and the like, but the zirconium oxide can only absorb ultraviolet light when absorbing light. In order to improve the light absorption efficiency of the zirconia and expand the application in the light absorption field, L.Renuka et al (L.Renuka, K.S.Anantharaju, S.C.Sharma, H.P.Nagaskura, S.C.Prashatha, H.Nagabhushana, Y.S.Vidya, Journal of Alloys and Compounds 672(2016)609 and 622.) adopt a low-temperature combustion method to prepare the magnesium-doped zirconia nano-particles, thereby greatly improving the surface area of the material, simultaneously forming a doping energy level in an energy band structure and reducing the forbidden band width so as to improve the light absorption rate; fakhri et al (A.Fakhri, S.Behrouz, I.Tyagi, S.Agarwal, V.K.Gupta, Journal of molecular Liquids 216(2016)342-346.) adopt a sol-gel method to prepare carbon-doped zirconia nanoparticles, realize the absorption of visible light by zirconia, and the absorption edge of the carbon-doped zirconia nanoparticles is about 415 nm. However, in practical application, the granular material is not beneficial to the recovery and reuse of the material, so Jiang et al (W.Jiang, J.He, J.Zong, J.Lu, S.Yuan, B.Liang, Applied Surface Science 307(2014)407-413.) adopt an anodic oxidation method to prepare the zirconia nanotube film, the light absorption edge of the film is about 300nm, the film still belongs to the ultraviolet light range, and the degradation rate of methyl orange under the ultraviolet light reaches 94.5% after 4 hours; bashirom, n. (Bashirom, N.; Kian, t.w.; Kawamura, g.; Matsuda, a.; Razak, k.a.; Lockman, z., Nanotechnology 2018,29.) et al, prepared by anodic oxidation, have a forbidden band width of 6.0-6.5eV and, after 2 hours of sunlight, have a photoreduction rate of hexavalent chromium in a solution having a pH of 2 of about 70%. Therefore, the zirconium oxide has certain light absorption performance and photocatalytic performance despite of wide intrinsic forbidden band width, and is expected to be a catalytic material with excellent performance after special treatment.
Disclosure of Invention
The invention aims to solve the problem that a white zirconia material with a wide forbidden band is changed into a black zirconia material with a narrow forbidden band, so that the specific surface area of the material is greatly improved, and the position of a high conduction band of the material is maintained.
The technical scheme of the invention is to provide a narrow-forbidden-band black zirconia nanotube film, wherein the optical forbidden band width of the black zirconia nanotube film is 1.0-3.0 eV.
Preferably, the content of fluorine atoms contained in the black zirconia nanotube film is 0 at.% to 4 at.%. More preferably from 1 at.% to 3 at.% (atomic percent).
Preferably, the thickness of the black zirconia nanotube film is 3-7 μm; the length of the nano tube in the black zirconia nano tube film is 3-7 mu m, the wall thickness of the nano tube is 5-30nm, and the tube diameter is 30-100 nm.
Preferably, the zirconia in the black zirconia nanotube film is a mixed phase structure of tetragonal phase and monoclinic phase.
The invention also provides a preparation method of the narrow-forbidden-band black zirconia nanotube film, which comprises the following steps:
(1) taking an inert electrode as a cathode and a polished zirconium sheet as an anode, and carrying out anodic oxidation in fluorine-containing electrolyte to prepare a zirconium oxide nanotube film;
(2) and cleaning the zirconia nanotube film, drying, and performing heat treatment in a protective atmosphere or a vacuum atmosphere at the temperature of 400-800 ℃ to obtain the narrow-bandgap black zirconia nanotube film.
Preferably, the protective atmosphere is an argon atmosphere.
Preferably, the electrolyte containing fluorine is an electrolyte containing ammonium fluoride and hydrofluoric acid.
Preferably, the fluorine-containing electrolyte is prepared by the following method: adding ammonium fluoride, hydrofluoric acid with the mass fraction of 40% and deionized water into glycerol, wherein the volume ratio of the glycerol to the hydrofluoric acid with the mass fraction of 40% to the deionized water is 100: (0.1-5): (1-25); the concentration of ammonium fluoride in the electrolyte is 0.1-0.35 mol/L.
Preferably, the time of the heat treatment is 2 to 4 hours.
Preferably, the temperature of the heat treatment is 500-.
The invention prepares the zirconia nanotube film with crystal lattice oxygen partially substituted by fluorine by an anodic oxidation method, and then carries out heat treatment at a lower temperature in an oxygen-free environment to remove all or part of fluorine and form a large number of oxygen vacancies. Wherein, the higher the heat treatment temperature is, the easier the fluorine is removed, and 600 ℃ can ensure that all fluorine atoms are removed. But experiments show that part of the fluorine-doped black zirconia nanotube film has better photocatalytic performance.
One of the great advantages of the invention is that the zirconium oxide nanotube film is subjected to heat treatment at a lower temperature in a protective atmosphere. Avoiding higher treatment temperature in non-reducing atmosphere or using thermite reaction for treatment.
Preferably, the anodizing conditions are: the preparation is carried out under the conditions of constant voltage of 20-60V and constant temperature of 20-30 ℃ and stirring for 0.5-12h by a direct current power supply.
The material of the invention can not only maintain the stability and the negative conduction band position of the zirconia, so that the zirconia has strong reduction potential, but also reduce the forbidden bandwidth of the zirconia, improve the light absorption performance of the zirconia and greatly improve the utilization rate of the zirconia to sunlight; the prepared zirconia film has a nanotube structure and excellent surface physicochemical characteristics of a pore structure, and the surface activity and the physicochemical adsorption capacity of zirconia are greatly improved by annealing treatment in an anoxic environment. The narrow-forbidden-band black zirconia nanotube film can be widely applied to various fields using sunlight, and has the following basic characteristics:
(1) the film material is ZrO2A mixed phase structure comprising tetragonal and monoclinic phases, a fluorine content of 0 at.% to 4 at.% (atomic percent), and a proportion of surface oxygen vacancies of 20% to 55%;
(2) the appearance of the film material is black;
(3) the zirconia is in a nanotube form, the length of the zirconia nanotube is 3-7 mu m, the wall thickness of the nanotube is 5-30nm, the pipe diameter (inner diameter) is 30-100nm, and the nanotubes are orderly arranged in a honeycomb shape;
(4) the optical forbidden band width of the film is 1.0-3.0eV, the absorption of light belongs to the full wave band range, wherein the absorption of ultraviolet and visible light wave bands is strongest;
(5) the thickness of the film is 3-7 μm.
The invention has the advantages that:
(1) compared with TiO2 material, it has more negative conduction band position, i.e. has strong reduction potential, and can improve the generation efficiency of superoxide radical in the photocatalysis process, thereby improving the efficiency of photocatalytic degradation of pollutants. (ii) a
(2) The prepared black zirconia nanotube film with narrow forbidden band has excellent absorption performance to ultraviolet light and high absorption to visible light, and changes the property that the traditional zirconia can not absorb the visible light, thereby improving the utilization rate of sunlight and expanding the application range;
(3) the prepared black zirconia nanotube film with narrow forbidden band exists in the form of a film/metal substrate, can be applied to the field of photocatalysis, solves the problem of recovery of a nano catalyst, and belongs to an environment-friendly high-performance material;
(4) the prepared black zirconia nanotube film with narrow forbidden band has a porous structure, large specific surface area, many surface defects, high surface activity, strong adsorption capacity to degraded substances, high-efficiency catalytic performance and repeated use capacity;
(5) under the irradiation of visible light, the efficiency of degrading organic matters such as rhodamine B by the narrow-gap black zirconia nanotube film is high, the degradation efficiency is not reduced after repeated times, and the traditional zirconia, titanium dioxide and the like can be degraded only under the irradiation of ultraviolet light.
(6) The fluorine-containing electrolyte is adopted to carry out anodic oxidation to prepare the zirconium oxide nanotube film, the equipment is simple, and large-area films can be prepared in a large scale;
(7) adopting fluorine-containing electrolyte to carry out anodic oxidation to prepare a zirconium oxide nanotube film, and carrying out in-situ fluorine doping on zirconium oxide;
(8) annealing in argon is adopted, the temperature is only 400-800 ℃, and is greatly lower than the temperature of more than 1000 ℃ for preparing the black zirconia in the reducing atmosphere;
(9) the prepared black zirconia nanotube film with narrow forbidden band has stable appearance.
Drawings
Fig. 1 is an SEM image of a black zirconia nanotube narrow bandgap film.
Fig. 2 is a TEM image of a black zirconia nanotube narrow bandgap film.
Fig. 3 is an XRD pattern of the black zirconia nanotube narrow bandgap film.
FIG. 4 is a DRS diagram of a black zirconia nanotube narrow bandgap film.
Fig. 5 is a graph of the effect of black zirconia nanotube narrow bandgap films on rhodamine B degradation under visible light conditions.
Fig. 6 shows the result of rhodamine B degradation by the black zirconia nanotube narrow bandgap film repeated five times under visible light conditions.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1: preparation of zirconia nanotube film
(1) Selecting a zirconium sheet with the diameter of 23mm, and mechanically polishing the zirconium sheet to a mirror surface to be used as an anode oxidation raw material;
(2) adding 0 vol% of hydrofluoric acid (analytically pure, 40%), 0.35mol/L of ammonium fluoride and 1 vol% of deionized water into glycerol (analytically pure, 99%), and uniformly stirring to obtain an anodic oxidation electrolyte A for later use; 0 vol% of hydrofluoric acid (analytically pure, 40%), 0.35mol/L of ammonium fluoride and 10 vol% of deionized water are added into glycerol (analytically pure, 99%), and the mixture is uniformly stirred to serve as anodic oxidation electrolyte B for later use.
(3) A two-electrode system is adopted, graphite flakes are used as cathodes, zirconium flakes are used as anodes, and anodic oxidation is respectively carried out in electrolyte A and electrolyte B. Keeping the temperature at 25 ℃, and preparing the anode oxide by adding magnetic stirring electrolyte for 2 hours. Wherein, when the electrolyte A is adopted, the constant voltage of a direct current power supply is 50V; when the electrolyte B is adopted, the direct current power supply has a constant voltage of 20V.
(4) And (3) washing the prepared anodic zirconia nano-tube film with deionized water, and drying for 2h at 80 ℃.
(5) The appearance of the zirconia nanotube film is represented by a field emission scanning electron microscope, the film prepared by the electrolyte A is 4 mu m thick, the wall thickness of the tube is about 25nm, and the tube diameter is about 30 nm; the thickness of the film prepared by the electrolyte B is 4 μm, the wall thickness of the tube is about 10nm, and the tube diameter is about 50nm.
Example 2: preparation of narrow forbidden band black zirconia nanotube film
(1) Selecting a zirconium sheet with the diameter of 23mm, and mechanically polishing the zirconium sheet to a mirror surface to be used as an anode oxidation raw material;
(2) 2 vol% of hydrofluoric acid (analytically pure, 40%), 0.35mol/L of ammonium fluoride (solid) and 2.5 vol% of deionized water are added into glycerol (analytically pure, 99%) and stirred uniformly to serve as an anodic oxidation electrolyte.
(3) A two-electrode system is adopted, a graphite sheet is used as a cathode, a zirconium sheet is used as an anode, a direct-current power supply has a constant voltage of 50V and a constant temperature of 25 ℃, and magnetic stirring electrolyte is used for carrying out anodic oxidation preparation for 2 hours.
(4) And (3) washing the prepared anodic zirconia nano-tube film with deionized water, and drying for 2h at 80 ℃.
(5) And (3) respectively carrying out heat treatment and heat preservation on the dried zirconia nanotube film at 500 ℃ and 800 ℃ in an argon atmosphere for 2h, then cooling to room temperature along with the furnace, and completing the preparation to obtain the black zirconia nanotube film with narrow forbidden band.
(6) The shapes of the zirconia nanotube films before and after annealing (heat treatment) are represented by a field emission scanning electron microscope and a transmission electron microscope, the thickness of the film before annealing is about 5 mu m, the wall thickness of the tube is about 10nm, and the tube diameter is about 80nm, as shown in figures 1 and 2; the thickness is about 5 μm after annealing at 500 ℃, the wall thickness of the tube is about 10nm, and the tube diameter is about 80 nm; the thickness is about 5 μm after annealing at 800 ℃, the wall thickness of the tube is about 25nm, and the tube diameter is about 50 nm; the phase structure of the annealed zirconia nanotube film is characterized by an X-ray diffractometer, and is a mixture of a tetragonal phase and a monoclinic phase, as shown in FIG. 3.
Example 3
(1) The anodic zirconia nanotube film prepared in the steps (1) to (4) in the example 2 is respectively subjected to heat treatment and heat preservation for 2 hours at 500 ℃, 600 ℃ and 800 ℃ in an argon atmosphere, and then is cooled to room temperature along with the furnace, so that the preparation is completed, and the narrow forbidden band black zirconia nanotube film is obtained.
(2) The black zirconia nanotube film annealed at 500 ℃ is characterized by adopting ultraviolet diffuse reflection absorption spectrum, the maximum absorption peak of the black zirconia nanotube film is about 384nm, the absorption edge is about 568nm, and the optical forbidden bandwidth is 2.35eV, as shown in FIG. 4; after annealing at 600 ℃, the maximum absorption peak of the black zirconia nanotube film is about 325nm, the absorption edge is about 525nm, and the optical forbidden bandwidth is 2.9 eV; the black zirconia nanotube film after annealing at 800 ℃ has the maximum absorption peak of about 436nm, has absorption in the full visible light range and the optical forbidden bandwidth of 1.5 eV.
Example 4
(1) The anodic zirconia nanotube film prepared in the steps (1) to (4) in the example 2 is respectively subjected to heat treatment and heat preservation for 2 hours at 500 ℃ and 550 ℃ under the argon atmosphere, and then is cooled to room temperature along with the furnace, so that the preparation is completed, and the narrow forbidden band black zirconia nanotube film is obtained.
(2) By X-ray photoelectron spectroscopy analysis, the fluorine content of the zirconium oxide nanotube film annealed at 500 ℃ is 2.6 at%, and the fluorine content of the zirconium oxide nanotube film annealed at 550 ℃ and 800 ℃ is 0 at%. By performing peak-splitting fitting on the oxygen 1s peaks of the two samples, and calculating the surface oxygen vacancy concentration as vacancy oxygen peak area/(vacancy oxygen peak area + lattice oxygen peak area) by adopting a formula, the proportion of oxygen vacancies on the surface of the zirconium oxide nanotube film annealed at 500 ℃ is 37%, the proportion of oxygen vacancies on the surface of the zirconium oxide nanotube film annealed at 550 ℃ is 51%, and the proportion of oxygen vacancies on the surface of the zirconium oxide nanotube film annealed at 800 ℃ is 31%.
Example 5
(1) 5mg of rhodamine B was weighed, dissolved in 1L of deionized water, and stirred uniformly to obtain a 5mg/L rhodamine B solution.
(2) The black zirconia nanotube film obtained by heat treatment in argon atmosphere at 500 ℃ in example 2 was placed in a beaker containing 5mL of the solution in step 1, and left to stand in the dark for 1 hour to allow the film and the solution to reach adsorption equilibrium.
(3) Irradiating by a commercial 50W LED lamp, carrying out visible light photocatalytic degradation at an irradiation distance of 10cm, detecting rhodamine B dissolution every half an hour, and carrying out photocatalytic reaction for 120 min.
(4) The absorbance was measured at a wavelength of 553nm with an ultraviolet-visible spectrophotometer toDeionized water was used as a reference. The concentration C of rhodamine B is proportional to the absorbance A, using Ct/C0Calculation of the photocatalytic degradation efficiency, C0Is the initial concentration C in step 1tThe concentrations were after 1h of dark treatment and after light irradiation.
(5) After dark treatment for 1h, the adsorption degradation efficiency of the narrow-forbidden-band black zirconia nanotube film on rhodamine B reaches 35 percent; after 120min of illumination, the narrow-bandgap black zirconia nanotube film degraded rhodamine B by 83% through two stages of adsorption and photocatalysis, while the purchased zirconia powder has no degradation effect, as shown in FIG. 5.
Example 6
(1) The sample subjected to the photocatalytic degradation experiment in example 4 was repeatedly washed with deionized water and dried in an oven at 80 ℃ for 8 hours.
(2) The dried sample is repeated with the steps (2) to (4) in the example 3, and the efficiency of the second sample for photodegradation of rhodamine B is obtained.
(3) Repeating the steps (1) and (2), and obtaining the efficiency of photodegrading rhodamine B of the third, fourth and fifth samples.
(4) The degradation efficiency of the sample after repeated photocatalytic degradation of rhodamine B for four times is obtained as follows: 81.5%, 81%, 80% as shown in FIG. 6.
Example 7
(1) 10mg of tetracycline hydrochloride was weighed, dissolved in 1L of deionized water, and stirred uniformly to obtain 10mg/L tetracycline hydrochloride solution.
(2) The black zirconia nanotube film of example 4 was placed in a beaker containing 5mL of the solution from step 1 above and allowed to stand in the dark for 1h to allow the film and solution to reach adsorption equilibrium.
(3) Irradiating with a 300W xenon lamp, filtering out light waves with the wavelength less than 420nm by using a 420nm optical filter, wherein the irradiation distance is 10cm, so that visible light photocatalytic degradation can be realized, and the photocatalytic reaction can be carried out for 120 min.
(4) The absorbance was measured at 357nm using an ultraviolet-visible spectrophotometer with deionized water as a reference. The concentration C of tetracycline hydrochloride is in direct proportion to the absorbance A, and C is usedt/C0Calculation of the photocatalytic degradation efficiency, C0Is the initial concentration C in step 1tThe concentrations were after 1h of dark treatment and after light irradiation.
(5) After dark treatment for 1h, the adsorption degradation efficiency of the narrow-forbidden-band black zirconia nanotube film on tetracycline hydrochloride is about 8%; after 120min of illumination, the narrow-band black zirconia nanotube film degrades tetracycline hydrochloride by 58% through two stages of adsorption and photocatalysis.
Claims (9)
1. The narrow-forbidden-band black zirconia nanotube film is characterized in that the optical forbidden band width of the black zirconia nanotube film is 1.0-3.0 eV; the black zirconia nanotube film with crystal lattice oxygen vacancy is prepared by an anodic oxidation method and heat treatment defluorination in an oxygen-free environment, the proportion of the surface oxygen vacancy is 20-55%, and zirconia in the black zirconia nanotube film is a mixed phase structure of tetragonal phase and monoclinic phase.
2. The narrow bandgap black zirconia nanotube film of claim 1, wherein the black zirconia nanotube film comprises fluorine atoms in an amount of from 0 at.% to 4 at.%.
3. The narrow bandgap black zirconia nanotube film of claim 1, wherein the black zirconia nanotube film has a thickness of 3-7 μm; the length of the nano tube in the black zirconia nano tube film is 3-7 mu m, the wall thickness of the nano tube is 5-30nm, and the tube diameter is 30-100 nm.
4. A preparation method of a narrow forbidden band black zirconia nanotube film is characterized by comprising the following steps:
(1) taking an inert electrode as a cathode and a polished zirconium sheet as an anode, and carrying out anodic oxidation in fluorine-containing electrolyte to prepare a zirconium oxide nanotube film;
(2) and cleaning the zirconia nanotube film, drying, and performing heat treatment under the conditions of a protective or vacuum atmosphere and a temperature of 400-800 ℃ to obtain the narrow-bandgap black zirconia nanotube film.
5. The method of claim 4, wherein the protective atmosphere is an argon atmosphere.
6. The method according to claim 4, wherein the fluorine-containing electrolyte is an electrolyte containing ammonium fluoride and hydrofluoric acid.
7. The method of claim 4, wherein the fluorine-containing electrolyte is formulated as follows: adding ammonium fluoride, hydrofluoric acid with the mass fraction of 40% and deionized water into glycerol, wherein the volume ratio of the glycerol to the hydrofluoric acid with the mass fraction of 40% to the deionized water is 100: (0-5): (1-25); the concentration of ammonium fluoride in the electrolyte is 0.1-0.35 mol/L.
8. The method of claim 4, wherein the anodizing conditions are: the preparation is carried out under the conditions of constant voltage of 20-60V and constant temperature of 20-30 ℃ and stirring for 0.5-12h by a direct current power supply.
9. The method of claim 4, wherein the heat treatment time is 2 to 4 hours.
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