CN114411190A - Preparation method and application of rare earth cerium doped titanium dioxide nanotube array structure material - Google Patents

Preparation method and application of rare earth cerium doped titanium dioxide nanotube array structure material Download PDF

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CN114411190A
CN114411190A CN202210139590.0A CN202210139590A CN114411190A CN 114411190 A CN114411190 A CN 114411190A CN 202210139590 A CN202210139590 A CN 202210139590A CN 114411190 A CN114411190 A CN 114411190A
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etching
titanium sheet
titanium
titanium dioxide
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陈燕鑫
童美虹
林世伟
卢灿忠
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Xiamen Institute of Rare Earth Materials
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/38—Alkaline compositions for etching refractory metals
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

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Abstract

The invention discloses a preparation method and application of a rare earth cerium doped titanium dioxide nanotube array structure material. A series of characterization and photoelectrocatalysis performance tests are carried out on the prepared cerium modified titanium dioxide photo-anode material, and the fact that the cerium modified titanium dioxide photo-anode material has excellent photoelectrocatalysis performance is found, and the photocurrent is greatly improved. The method enhances the absorption of visible light wavelength under bias voltage, improves the utilization rate of sunlight, has simple synthesis method, easily controlled reaction conditions and stable chemical properties, provides a brand new thought for better and more convenient modified titanium dioxide to promote the research on the photoelectric catalytic performance, and has wider application prospect.

Description

Preparation method and application of rare earth cerium doped titanium dioxide nanotube array structure material
Technical Field
The invention relates to a preparation method and application of a rare earth cerium doped titanium dioxide nanotube array structure.
Background
Current global energy consumption remains largely dependent on fossil fuels, with large carbon dioxide emissions leading to global warming and climate change. The energy shortage, the development difficulty and the cost are increased sharply due to excessive energy development, low energy utilization rate and the like. Meanwhile, the demand of world economic development on energy is increasing day by day; carbon neutralization and reduction of carbon emissions have been advocated worldwide. As the first major world population, china is finding clean and renewable energy sources to reduce carbon dioxide emissions.
Converting solar energy to hydrogen energy is a significantly attractive and sustainable solution to energy and environmental problems. The hydrogen can not discharge greenhouse gas after combustion, and the atmospheric environment can not be polluted by aerosol, fine particles and the like. Limited by the current technical development, the hydrogen production cost is still high, petrochemical energy is mainly used for reforming hydrogen production, and emission pollution is still difficult to treat in the hydrogen preparation process. Compared with the traditional hydrogen production scheme, the photocatalysis can directly utilize solar energy as a light source to drive reaction, and is an ideal environment pollution treatment technology and clean energy production technology.
Fujishima and Honda find that since photoelectrochemical decomposition of water obtains hydrogen and oxygen, semiconductor photocatalyst hydrolysis to produce hydrogen becomes an important strategy for converting solar energy into hydrogen energy. On one hand, the photoelectrocatalysis hydrolysis hydrogen production can solve the problem of energy shortage, and on the other hand, the photoelectrocatalysis hydrolysis hydrogen production can also effectively control the environment.
Metal oxide-based photoanode design and construction is one of the promising strategies for enabling PEC cells to have a breakthrough in solar to hydrogen conversion efficiency. Currently, photo-anode electrolytic cells are mainly used, and therefore, a series of photocatalytic n-type semiconductor anode materials have been designed and prepared for efficient conversion of solar energy. Good photoanode materials generally have the following conditions: the preparation cost is low, the chemical stability is good, the environment is friendly, the carrier migration rate is high, the interface charge transfer is rapid, the positions of a conduction band and a valence band need to be met, and the light stability of the material is determined by the electronic property of the edge of an energy band to a certain extent.
Compared with other metal oxide semiconductors, titanium dioxide is currently the most promising semiconductor material for applications and fundamental research. Titanium dioxide, a typical n-type semiconductor, has been widely studied as a photoanode for the decomposition of PEC water due to its advantages of suitable band edge positioning, low cost, non-toxicity, good stability, and convenient preparation. However, titanium dioxide itself still has some inherent drawbacks such as poor visible light absorption due to wide bandgap, fast carrier recombination, low electronic conductivity, etc., which greatly limit its performance enhancement in practical PEC water splitting applications.
The titanium dioxide nanotube array shows good directional charge transport characteristics, and overcomes the defects of free electron scattering expansion and electron mobility reduction caused by structural disorder of the nano-particle titanium dioxide at the contact position of two crystal particles. The electrochemical anode oxidation method has the advantages of single-process tube manufacturing, uniform and ordered nanotube structure preparation, easy control of the size and the shape of the nanotube and the like. In order to expand the band gap absorption range of the titanium dioxide nanotube from an ultraviolet region to a visible light region and improve the visible light response range of the titanium dioxide, the titanium dioxide nanotube is modified by selectively adding rare earth elements.
The invention prepares the rare earth cerium doped titanium dioxide nanotube photoelectric anode structure by a secondary anodic oxidation method, shows good visible light absorption performance in a PEC electrolytic cell, and improves the light conversion efficiency. The modification is directly carried out in the etching process, the rare earth elements are doped, the doping method is simple and convenient, and the modification requirement can be met without particularly complicated steps. The electrochemical anode oxidation method for preparing the metal oxide two-dimensional ordered array has low cost and simple operation, does not need complex experimental equipment and harsh experimental conditions, and the metal oxide two-dimensional ordered array prepared in a single batch has 9 pieces in one batch, is uniform and has good repeatability. Provides a new idea for optimizing the photoelectrochemical property of the titanium dioxide photo-anode and has better application prospect.
Disclosure of Invention
The purpose of the invention is: aiming at the problems of poor visible light absorption, rapid carrier recombination, low electronic conductivity and complicated preparation of the existing titanium dioxide material serving as a photoelectric catalyst, the cerium-doped titanium dioxide nanotube is prepared by adopting a secondary anodic oxidation method, synchronous doping in the etching process is directly realized, the method is simple, the reproducibility is good, and the photoelectric catalytic performance is excellent.
In order to achieve the purpose, the technical scheme for obtaining the rare earth cerium doped titanium dioxide nanotube photo-anode comprises the following steps:
1) titanium sheet pretreatment: ultrasonic cleaning titanium sheet with soap water and acetone for no less than 30 min, rinsing titanium sheet with anhydrous ethanol and ultrapure water for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium sheet into an oven to be dried for not less than 30 min to obtain the titanium sheet with clean and dry surface.
2) A titanium sheet film pasting step: placing the paper patterns which are designed into 9 pieces with the size of 1 multiplied by 1cm and accord with the size of the titanium sheet on a glass watch glass for pasting, pasting an adhesive tape layer on the paper patterns, cutting the adhesive tape by a blade and a ruler, pasting the cut adhesive tape on the titanium sheet with clean and dry surface prepared in the step 1), and obtaining the titanium sheet pasted with the adhesive tape.
3) Etching liquid preparation: preparing three different etching liquids:
etching liquid I: weighing ammonium fluoride, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h to obtain an etching solution I containing 0.36 wt% of ammonium fluoride and 1.8 vol% of ultrapure water.
Etching liquid II: weighing ammonium fluoride and cerous nitrate hexahydrate, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h to obtain an etching solution II containing 0.36 wt% of ammonium fluoride, 0.01 wt% of cerous nitrate hexahydrate and 1.8 vol% of etching solution II.
Etching liquid III: weighing ammonium fluoride and cerous nitrate hexahydrate, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h to obtain an etching solution III containing 0.36 wt% of ammonium fluoride, 1.0 wt% of cerous nitrate hexahydrate and 1.8 vol% of etching solution III.
4) The preparation method of the electrochemical anodic oxidation one-time etching doping comprises the following steps: fixing the titanium sheet stuck with the adhesive tape prepared in the step 2) on an anodeSelecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm, setting the voltage to be 60V, and firstly carrying out primary etching by using the etching solution prepared in the step 3), wherein the etching time is 1 h; after etching is finished, ultrasonically cleaning the grown titanium tube for 30 min to leave a titanium sheet substrate; then rinsing the titanium sheet substrate with absolute ethyl alcohol and ultrapure water respectively for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium plate into an oven to be dried for not less than 30 min to obtain the titanium plate substrate with a clean and dry surface for secondary etching.
5) The preparation method comprises the following steps of electrochemical anodic oxidation secondary etching doping: fixing the titanium sheet substrate with the clean and dry surface prepared in the step 4) on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 10-20 mm, setting the voltage to be 60V, and carrying out secondary etching by using the etching liquid II prepared in the step 3), wherein the etching time is 1 h 30 min; after the etching of the etching solution II is finished, soaking the substrate in an ethylene glycol solution for 12 hours; tearing off the adhesive tape on the surface, then annealing in air at 400 ℃ for 2 h, wherein the heating rate is not higher than 1 ℃/min, and obtaining the cerium-doped titanium dioxide nanotube array structure photoelectrocatalysis material with the concentration of 0.01%. The marker was 0.01% Ce-TNT. Simultaneously, annealing under the same condition, and etching and doping 1% concentration cerium ions by the etching solution which is prepared in the step 3) by using the etching solution for three purposes, wherein the mark is 1% Ce-TNT; the blank titanium tube was annealed under the same conditions and labeled TNT.
The rare earth cerium doped titanium dioxide nanotube prepared by the invention is applied to the solar energy conversion process, such as being used as a photo-anode and other reference samples to test the electrochemical parameters.
Compared with the prior art, the implementation mode has the following characteristics:
at present, the modification and the coating of the titanium dioxide are mainly carried out after etching, the common scheme of in-situ treatment is to etch on a titanium/other metal alloy substrate, the limit is large by adjusting the alloy proportion to change the doping content, so the modification and the doping of rare earth elements are directly carried out in the etching process. The doping method is simple and convenient, and can meet the modification requirement without particularly complicated steps. According to the invention, pure titanium is adopted as the substrate of the photo-anode by a secondary anodic oxidation method, and trace cerium ions are loaded on the titanium tube in the etching process to prepare the rare earth cerium doped titanium dioxide nanotube, and the rare earth cerium doped titanium dioxide nanotube has good visible light absorption performance. The method is simple and easy to prepare, can be used for large-scale preparation, has excellent photoelectric catalytic performance, and provides a new method and thought for doping modification of the titanium dioxide nanotube by other ions.
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The following description of the main parameter features of the present invention is illustrated by the figures
FIG. 1 is a flow chart of the present invention for preparing a rare earth cerium doped titanium dioxide nanotube array structure photoelectrocatalysis material.
FIG. 2 is a diagram of an apparatus for preparing a rare earth cerium doped titanium dioxide nanotube array structure photocatalytic material according to the present invention.
FIG. 3 is a paper pattern of the rare earth cerium doped titanium dioxide nanotube array structure of the present invention.
FIG. 4 is a FEI-SEM field emission scanning electron microscope image; in the figure, a) is a FEI-SEM field emission scanning electron microscope picture of TNT. b) The figure is a FEI-SEM field emission scanning electron microscope image of 0.01% Ce-TNT. c) FIG. is a FEI-SEM field emission scanning electron micrograph of 1% Ce-TNT. The result shows that the addition of cerium ions in the formula of the etching solution does not affect the tubular shape of the titanium dioxide, and the cerium ions are successfully doped by the simple method.
FIG. 5 is an XRD spectrum of TNT, 0.01% Ce-TNT, and 1% Ce-TNT. The results show that 0.01% Ce doped TNT has a shift in peak profile around 25 °, and 1% Ce doped TNT has a pronounced ceria peak.
FIG. 6 is an X Photoelectron Spectrum (XPS) showing that Ce is Ce on a titanium tube4+In the form, when the loading amount of cerium element is 0.01%, metal peaks Ti 2P and O1S are shifted relative to an original titanium tube, and a metal peak Ce 3d has a little peak type; when the loading amount of the cerium element is 1%, the peak type of the cerium is obvious.
FIG. 7 is a graph of the photocurrent densities of a photo-anode TNT, 0.01% Ce-TNT, and 1% Ce-TNT compared at different potentials, tested using a three-electrode system, with Pt as the counter electrode,the reference electrode was Ag/AgCl in 0.1M Na2SO4The solution is an electrolyte. Under the condition of 1.45V vs. Ag/AgCl, the photocurrent densities of the TNT, the 0.01 percent Ce-TNT and the 1 percent Ce-TNT under the full spectrum are respectively 0.45 mA/cm, 3 mA/cm and 0.9 mA/cm2This shows that the trace cerium element doped in the titanium dioxide nanotube array material exerts excellent photocatalytic performance.
FIG. 8 is a graph comparing the photocurrent densities of the photoanode TNT, 0.01% Ce-TNT, and 1% Ce-TNT at a constant potential of 1.35V vs. RHE. The result shows that the photocurrent density is 0.01 percent of Ce-TNT > > TNT and 1 percent of Ce-TNT, and the stability is better.
Fig. 9 shows the constant potential wavelength scanning photocurrent density and the photoelectric conversion efficiency, the left graph shows the wavelength scanning photocurrent density, and the right graph shows the corresponding photoelectric conversion efficiency, and the results show that the 0.01% Ce-TNT photoanode can generate photocurrent within the visible light range under bias voltage compared with the rest photoanodes, the light absorption edge extends to 550 nm, and the light conversion efficiency reaches 110% at 390 nm.
Fig. 10 is a result of calculating a band gap according to photoelectric conversion efficiency (IPCE), and the result shows that after 0.8V bias is applied, the band gap of the rare earth cerium doped titanium dioxide nanotube 0.01% Ce-TNT is 2.843 eV, which reduces the band gap and is beneficial to improving the photoelectric conversion efficiency.
FIG. 11 is a Mott-Schottky curve test, and Mott-Schottky results show that the 0.01% Ce-TNT of the rare earth cerium doped titanium dioxide nanotubes has a flat band potential of about-0.044V (vs. RHE PH = 6) and possesses a flat band position more favorable for photoelectron transport.
FIG. 12 is an impedance diagram (EIS), and the result shows that the impedance of 0.01% Ce-TNT of the rare earth cerium-doped titanium dioxide nanotube is smaller than that of the rest photo-anode, which is beneficial to the transmission of photo-generated carriers.
Detailed Description
In the invention, a secondary anodic oxidation method is adopted, the characteristic of rare earth ion photoconversion is utilized, cerium is loaded on a titanium tube, and the rare earth cerium doped titanium dioxide nanotube photoanode for absorbing visible light is prepared.
Example 1
Preparation of TNT: ultrasonic cleaning titanium sheet with soap water and acetone for no less than 30 min, rinsing titanium sheet with anhydrous ethanol and ultrapure water for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium sheet into an oven to be dried for not less than 30 min to obtain the titanium sheet with clean and dry surface. The paper patterns which are designed to be divided into 9 pieces with the size of 1 multiplied by 1cm and accord with the size of the titanium sheet are placed on a glass watch and pasted, an adhesive tape layer is pasted on the paper patterns, the adhesive tape is cut by a blade and a ruler, and the cut adhesive tape is pasted on the titanium sheet with clean and dry surface. Fixing the prepared titanium sheet pasted with the adhesive tape on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm and the voltage to be 60V, carrying out primary etching by using prepared etching liquid I, and preparing the etching liquid I according to the proportion: 1.8 g of ammonium fluoride is weighed, 9 mL of ultrapure water is sucked, 500 mL of ethylene glycol is added, and the stirring time is not less than 12 h. The etching time is 1 h.
After etching is finished, ultrasonically cleaning the grown titanium tube for 30 min to leave a substrate; then rinsing the titanium sheet substrate with absolute ethyl alcohol and ultrapure water respectively for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium plate into an oven to be dried for not less than 30 min to obtain the titanium plate substrate with a clean and dry surface for secondary etching. Fixing a titanium sheet substrate with a clean and dry surface on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm and the voltage to be 60V, and etching by using the same etching liquid for 1 h 30 min; after etching, soaking in glycol solution for 12 h; and tearing off the adhesive tape on the surface, then carrying out air annealing at 400 ℃, keeping the temperature for 2 h, and obtaining the original TNT (blank titanium tube) at the heating rate of 0.8 ℃/min. The final sample obtained has uniform pore size.
Example 2
Preparation of 0.01% Ce-TNT: ultrasonic cleaning titanium sheet with soap water and acetone for no less than 30 min, rinsing titanium sheet with anhydrous ethanol and ultrapure water for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium sheet into an oven to be dried for not less than 30 min to obtain the titanium sheet with clean and dry surface. Dividing the design into 9 paper patterns of 1 × 1cm size meeting the size of titanium sheet, placing on a glass watch dish, and stickingAnd (3) pasting, namely pasting the adhesive tape layer on a paper pattern, cutting the adhesive tape by using a blade and a ruler, and pasting the cut adhesive tape on a titanium sheet with a clean and dry surface. Fixing the prepared titanium sheet pasted with the adhesive tape on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm and the voltage to be 60V, carrying out primary etching by using prepared etching liquid I, and preparing the etching liquid I according to the proportion: 1.8 g of ammonium fluoride is weighed, 9 mL of ultrapure water is sucked, 500 mL of ethylene glycol is added, and the stirring time is not less than 12 h. The etching time is 1 h.
After etching is finished, ultrasonically cleaning the grown titanium tube for 30 min to leave a substrate; then rinsing the titanium sheet substrate with absolute ethyl alcohol and ultrapure water respectively for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium plate into an oven to be dried for not less than 30 min to obtain the titanium plate substrate with a clean and dry surface for secondary etching. Fixing a titanium sheet substrate with a clean and dry surface at an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm and the voltage to be 60V, and preparing etching liquid II for the second etching: weighing 1.8 g of ammonium fluoride and 0.178 g of cerous nitrate hexahydrate, sucking 9 mL of ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h; etching time is 1 h 30 min; after etching, soaking in glycol solution for 12 h; tearing off the adhesive tape on the surface, then carrying out air annealing at 400 ℃, keeping the temperature for 2 h, and obtaining 0.01 percent Ce-TNT at the heating rate of 0.8 ℃/min. The aperture of the finally obtained sample is uniform, and trace doping of cerium is realized.
Example 3
Preparation of 1% Ce-TNT: ultrasonic cleaning titanium sheet with soap water and acetone for no less than 30 min, rinsing titanium sheet with anhydrous ethanol and ultrapure water for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium sheet into an oven to be dried for not less than 30 min to obtain the titanium sheet with clean and dry surface. The paper patterns which are designed to be divided into 9 pieces with the size of 1 multiplied by 1cm and accord with the size of the titanium sheet are placed on a glass watch and pasted, an adhesive tape layer is pasted on the paper patterns, the adhesive tape is cut by a blade and a ruler, and the cut adhesive tape is pasted on the titanium sheet with clean and dry surface. Fixing the prepared titanium sheet with the adhesive tape on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, and arranging the two electrodesThe distance is 20 mm, the voltage is set to be 60V, the prepared first etching solution is used for etching for one time, and the first etching solution is prepared according to the proportion: 1.8 g of ammonium fluoride is weighed, 9 mL of ultrapure water is sucked, 500 mL of ethylene glycol is added, and the stirring time is not less than 12 h. The etching time is 1 h.
After etching is finished, ultrasonically cleaning the grown titanium tube for 30 min to leave a substrate; then rinsing the titanium sheet substrate with absolute ethyl alcohol and ultrapure water respectively for at least 3 times, and rinsing with N2And after blowing and drying, putting the titanium plate into an oven to be dried for not less than 30 min to obtain the titanium plate substrate with a clean and dry surface for secondary etching. Fixing a titanium sheet substrate with a clean and dry surface at an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 20 mm and the voltage to be 60V, and preparing etching liquid III for the second etching: weighing 1.8 g of ammonium fluoride and 17.835 g of cerous nitrate hexahydrate, sucking 9 mL of ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h; etching time is 1 h 30 min; after etching, soaking in glycol solution for 12 h; tearing off the adhesive tape on the surface, then carrying out air annealing at 400 ℃, keeping the temperature for 2 h, and obtaining 1% Ce-TNT at the heating rate of 0.8 ℃/min.
Example 4
The constant potential photocurrent test was carried out on the TNT obtained in example 1, the 0.01% Ce-TNT obtained in example 2 and the 1% Ce-TNT obtained in example 3, using a xenon lamp simulated sunlight corrected by solar spectrum and having a light intensity of 100 mW/cm2The platinum sheet was used as the counter electrode, the Ag/AgCl electrode was used as the reference electrode, and the working electrodes were the photo-anodes prepared in examples 1, 2, and 3, respectively, each with 0.1M Na2SO4The solution was an electrolyte, a constant bias of 0.8V vs. Ag/AgCl was applied to the working electrode using the electrochemical workstation of CHI760E, and a photocurrent-time curve was recorded. The results showed that the photocurrent densities of TNT, 0.01% Ce-TNT and 1% Ce-TNT were 0.7, 2.1 and 0.5 mA/cm, respectively2It is demonstrated that 0.01% Ce-TNT can utilize solar energy more efficiently.
Example 5
The TNT obtained in example 1, the 0.01% Ce-TNT obtained in example 2, and the 1% Ce-TNT obtained in example 3 were subjected to a potentiostatic wavelength scanning photocurrent test, and simulated sunlight was applied to a xenon lamp to obtain a product having a high luminous efficiencyThe test was carried out using a three-electrode system with a platinum plate as the counter electrode, an Ag/AgCl electrode as the reference electrode, and the working electrodes being the photoanodes prepared in examples 1, 2, and 3, respectively, each with 0.1M Na2SO4The solution is electrolyte, the Wuhan Cisco special electrochemical workstation controls the electrochemical workstation to detect photocurrent generated under the irradiation of 300-600 nm wavelength spectrum under different constant potential conditions, and the scanning precision is 1 nm. The result shows that under the additional bias, the wavelength response interval of the 0.01% Ce-TNT photoanode is 300-550 nm, and the rest photoanodes have almost no photocurrent response under the visible light wavelength, which shows that the 0.01% Ce-TNT photoanode has visible light absorption capability and higher photogenerated carrier separation efficiency.
Example 6
The TNT prepared in example 1, the 0.01% Ce-TNT prepared in example 2, and the 1% Ce-TNT prepared in example 3 were subjected to a potentiostatic wavelength scanning photocurrent test, a xenon lamp was used to simulate sunlight, a three-electrode system was used to perform the test, a platinum sheet was used as a counter electrode, an Ag/AgCl electrode was used as a reference electrode, and working electrodes were the photoanodes prepared in examples 1, 2, and 3, respectively, each with 0.1M Na2SO4The solution is an electrolyte, and a Mott-Schottky curve is tested by a Wuhan Cisco special electrochemical workstation. The results show that the 0.01% Ce-TNT of the rare earth cerium doped titanium dioxide nanotube has a flat band potential of about-0.044V (vs. RHE PH = 6), and has a flat band position which is more beneficial to photoelectron transmission.
Example 7
The TNT prepared in example 1, the 0.01% Ce-TNT prepared in example 2, and the 1% Ce-TNT prepared in example 3 were subjected to a potentiostatic wavelength scanning photocurrent test, a xenon lamp was used to simulate sunlight, a three-electrode system was used to perform the test, a platinum sheet was used as a counter electrode, an Ag/AgCl electrode was used as a reference electrode, and working electrodes were the photoanodes prepared in examples 1, 2, and 3, respectively, each with 0.1M Na2SO4The solution is electrolyte, and EIS curve is tested by a Wuhan Cisco special electrochemical workstation. The result shows that the impedance of the 0.01 percent Ce-TNT of the rare earth cerium doped titanium dioxide nanotube is smaller than that of the rest photo-anode, which is beneficial to the transmission of photo-generated carriers.

Claims (2)

1. A preparation method of a rare earth cerium doped titanium dioxide nanotube array structure material is characterized by comprising the following steps:
1) titanium sheet pretreatment: ultrasonic cleaning titanium sheet with soap water and acetone for no less than 30 min, rinsing titanium sheet with anhydrous ethanol and ultrapure water for at least 3 times, and rinsing with N2Blowing and drying, and then putting into an oven to be dried for not less than 30 min to obtain a titanium sheet with a clean and dry surface;
2) a titanium sheet film pasting step: placing paper patterns which are designed to be divided into 9 pieces with the size of 1 multiplied by 1cm and accord with the size of a titanium sheet on a glass watch glass for pasting, pasting an adhesive tape layer on the paper patterns, cutting the adhesive tape by a blade and a ruler, pasting the cut adhesive tape on the titanium sheet with clean and dry surface prepared in the step 1), and obtaining the titanium sheet pasted with the adhesive tape;
3) etching liquid preparation: preparing three different etching liquids:
etching liquid I: weighing ammonium fluoride, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 h to obtain an etching solution I containing 0.36 wt% of ammonium fluoride and 1.8 vol% of ultrapure water;
etching liquid II: weighing ammonium fluoride and cerous nitrate hexahydrate, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 hours to obtain an etching solution II containing 0.36 wt% of ammonium fluoride, 0.01 wt% of cerous nitrate hexahydrate and 1.8 vol% of etching solution II;
etching liquid III: weighing ammonium fluoride and cerous nitrate hexahydrate, sucking ultrapure water, adding 500 mL of ethylene glycol, and stirring for not less than 12 hours to obtain an etching solution III containing 0.36 wt% of ammonium fluoride, 1.0 wt% of cerous nitrate hexahydrate and 1.8 vol% of etching solution III;
4) the preparation method of the electrochemical anodic oxidation one-time etching doping comprises the following steps: fixing the titanium sheet pasted with the adhesive tape prepared in the step 2) on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 10-20 mm, setting the voltage to be 60V, and firstly carrying out primary etching by using the etching liquid prepared in the step 3), wherein the etching time is 1 h; after etching is finished, carrying out ultrasonic treatment for 30 min, and then cleaning the grown titanium tube to leave a titanium sheet substrate; then rinsing the titanium sheet substrate with absolute ethyl alcohol and ultrapure water respectively for at least 3 times, and rinsing with N2After blowing and drying, putting the titanium plate into an oven to be dried for not less than 30 min to obtain a titanium plate substrate with a clean and dry surface for secondary etching;
5) the preparation method comprises the following steps of electrochemical anodic oxidation secondary etching doping: fixing the titanium sheet substrate with the clean and dry surface prepared in the step 4) on an anode, selecting a high-purity titanium sheet as a cathode counter electrode, setting the distance between the two electrodes to be 10-20 mm, setting the voltage to be 60V, performing secondary etching by using the etching liquid II or the etching liquid III prepared in the step 3), etching and doping 0.01% cerium ions by using the etching liquid II, etching and doping 1% cerium ions by using the etching liquid III, and etching for 1 h 30 min; after the etching of the second etching solution or the third etching solution is finished, soaking the second etching solution or the third etching solution in a glycol solution for 12 hours; tearing off the adhesive tape on the surface, then annealing in air at 400 ℃ for 2 h, wherein the heating rate is not higher than 1 ℃/min, and obtaining the cerium-doped titanium dioxide nanotube array structure photoelectric catalytic material with different concentrations.
2. The use of the cerium-doped titanium dioxide nanotube array structure photocatalytic material of different concentrations prepared in claim 1 in solar energy conversion processes.
CN202210139590.0A 2022-02-16 2022-02-16 Preparation method and application of rare earth cerium doped titanium dioxide nanotube array structure material Pending CN114411190A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106917128A (en) * 2017-03-10 2017-07-04 北京工业大学 A kind of tin molybdenum codope titanium dioxide nanotube array electrode and preparation method
CN111185148A (en) * 2020-02-21 2020-05-22 大连理工大学 Ce-Zn modified TiO2Preparation method and application of nanotube array composite catalytic material
CN111672502A (en) * 2020-05-21 2020-09-18 哈尔滨学院 Method for preparing lanthanum/manganese codoped titanium oxide nanotube with photocatalytic activity by anodic oxidation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106917128A (en) * 2017-03-10 2017-07-04 北京工业大学 A kind of tin molybdenum codope titanium dioxide nanotube array electrode and preparation method
CN111185148A (en) * 2020-02-21 2020-05-22 大连理工大学 Ce-Zn modified TiO2Preparation method and application of nanotube array composite catalytic material
CN111672502A (en) * 2020-05-21 2020-09-18 哈尔滨学院 Method for preparing lanthanum/manganese codoped titanium oxide nanotube with photocatalytic activity by anodic oxidation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JIAOJIAO GONG ET AL.: ""Electrochemically multi-anodized TiO2 nanotube arrays for enhancing hydrogen generation by photoelectrocatalytic water splitting"" *
JIN-YOUNG CHOI ET AL.: ""Fabrication of Au nanoparticle-decorated TiO2 nanotube arrays for stable photoelectrochemical water splitting by two-step anodization"" *
XIAO FAN ET AL.: ""High-efficiency photoelectrocatalytic hydrogen generation enabled by Ag deposited and Ce doped TiO2 nanotube arrays"" *

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