CN112661241B - High-efficiency titanium dioxide photoelectrode with {111} crystal face highly exposed and preparation and application thereof - Google Patents
High-efficiency titanium dioxide photoelectrode with {111} crystal face highly exposed and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a {111} crystal face high exposureThe preparation and application of the titanium dioxide high-efficiency photoelectrode comprises the following preparation processes: titanium mesh is used as a titanium source, hydrochloric acid is used as a morphology control agent, hydrogen peroxide is used as an oxidant, and one-dimensional vertical rutile TiO with exposed top {111} crystal faces grows in situ on a titanium mesh substrate through a gas phase hydrothermal method 2 The nano rod optimizes the {111} crystal face exposure proportion to be nearly 100% by adjusting the hydrothermal reaction time, and the {111} TiO is prepared 2 The Ti photoelectrode can be applied to deep removal of dimethyl phthalate (DMP) wastewater. Compared with the prior art, the {111} TiO prepared by the invention 2 The Ti high-efficiency photoelectrode adopts a titanium net as a titanium source, and the constructed {111} crystal face high-exposure one-dimensional titanium dioxide nanorod structure has high-efficiency photoelectrocatalytic oxidation capability and high stability and can be recycled.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis, and relates to a {111} crystal face high-exposure titanium dioxide efficient photoelectrode and preparation and application thereof.
Background
Phthalate esters (Phthalates esters, PAEs) are a class of synthetic chemicals that are widely used in polyvinyl chloride products, food packaging, coatings, toys and personal care products to increase the flexibility and extensibility of the products. Because PAEs are not chemically bound to the host plastic, they are readily released from the plastic article into the surrounding environment and even into the organism, thereby affecting the reproductive system of the organism and creating teratogenicity and carcinogenicity. Because of the high toxicity of PAEs, their contamination has received a great deal of attention, and many countries and regions place some of the PAEs on their focus on controlling contaminants. In China, dimethyl phthalate (DMP), diethyl phthalate (DEP) and dioctyl phthalate (DOP) have been identified as environmental priority contaminants, and some PAEs (such as dibutyl phthalate (DBP)) are also included in the drinking water source control standard. However, due to the large-scale production and application of PAEs, the detected concentration in municipal sewage often reaches μg/L, which is seriously threatening the safety of water and life health, so efficient removal of DMP in water is a hot spot subject in the current environmental water treatment field.
Titanium dioxide has the advantages of low cost, no toxicity, strong optical stability and the like, is one of semiconductor materials widely studied in recent decades, and has wide application prospect in the fields of photocatalysis, photoelectrocatalysis, solar cells and the like. Compared with anatase titanium dioxide widely used, rutile titanium dioxide is the most thermodynamically stable crystal form, and the application capacity of the rutile titanium dioxide is limited due to the fast recombination rate of photo-generated electron hole pairs. However, the band gap of rutile type titanium dioxide is narrower at room temperature, about 3.0eV, and the rutile type titanium dioxide can absorb visible light, and the problem of high recombination rate of photo-generated electron hole pairs can be effectively solved by applying bias voltage.
For example, chinese patent CN108911056A discloses a preparation method and application of a {001} crystal face controllable exposed titanium dioxide photoelectrode, which uses a titanium plate as a titanium source, hydrofluoric acid as a blocking agent, and in-situ grows TiO on a titanium substrate by a hydrothermal method 2 Flower-like microsphere structure with {001} crystal face exposure ratio of 0% -100%, and {001} TiO prepared 2 The Ti photoelectrode can be applied to the photoelectrocatalytic oxidative degradation of dimethyl phthalate wastewater. The patent has higher photoelectrocatalysis degradation performance, but has larger improvement space in the degradation and removal performance of pollutants such as dimethyl terephthalate and the like.
Disclosure of Invention
The invention aims to provide a {111} crystal face high-exposure titanium dioxide efficient photoelectrode and preparation and application thereof, which can obviously promote separation and transfer of photo-generated charges and effectively realize degradation and removal of dimethyl phthalate in a water body.
The aim of the invention can be achieved by the following technical scheme:
on one hand, the invention provides a preparation method of a {111} crystal face high-exposure titanium dioxide high-efficiency photoelectrode, which comprises the steps of using a titanium mesh as a titanium source, hydrochloric acid as a morphology control agent, hydrogen peroxide as an oxidant, and growing in situ on a titanium mesh substrate by a gas phase hydrothermal method, wherein the top end of the pyramid-shaped TiO is 2 Nano-rods to obtain {111} TiO with highly exposed {111} crystal face 2 And (3) Ti photoelectrode, namely the target product. The preparation process comprises the following steps: taking titanium net for chemical polishing, and then placing the titanium net above a mixed solution composed of hydrochloric acid, hydrogen peroxide and water for gas treatmentAnd carrying out phase hydrothermal reaction, cleaning and drying the obtained reacted sample, and calcining to obtain the target product.
Further, the chemical polishing process specifically comprises: the titanium mesh is placed in a mixed acid solution containing nitric acid, hydrofluoric acid and water for treatment.
Further, the volume ratio of nitric acid, hydrofluoric acid and water is 5:1:20 to 5:1:50, preferably 5:1:25.
Further, in the gas phase hydrothermal reaction process, the volume ratio of hydrochloric acid to hydrogen peroxide to water is 4:1:17-5:1:17, preferably 4.2:1:17; the mass fraction of the hydrochloric acid is 36-38%, and the mass fraction of the hydrogen peroxide is 30%.
Further, the temperature of the gas phase hydrothermal reaction is 180-220 ℃, preferably 200 ℃, and the time is 2-12 hours, preferably 5 hours.
Further, the specification of the titanium mesh is 60 to 100 mesh, preferably 80 mesh, and the distance between the titanium mesh and the liquid surface of the mixed solution is 5.5 to 6.5cm, preferably 6.0cm.
Further, the calcination is carried out in an air atmosphere, and the calcination temperature is 400-550 ℃, preferably 450 ℃; the calcination time is 1 to 3 hours, preferably 2 hours; the temperature rising rate in the calcination process is 1-5 ℃/min, preferably 3 ℃/min.
On the other hand, the invention also provides a {111} crystal face highly exposed titanium dioxide high-efficiency photoelectrode which is prepared by adopting the preparation method, and particularly the obtained TiO 2 The nanorod size is about 300-500 nm, and the exposure ratio of the {111} crystal face at the top is close to 100%.
In still another aspect, the invention also provides an application of the {111} crystal face high-exposure titanium dioxide high-efficiency photoelectrode for photoelectrocatalysis of dimethyl phthalate in water.
Further, in specific application, a three-electrode system is adopted, and {111} TiO is adopted respectively 2 A Ti photoelectrode, a platinum sheet, a saturated calomel electrode are used as a working electrode, a counter electrode and a reference electrode, 0.1mol/L sodium sulfate deionized water solution is used as electrolyte, and waste containing 2mg/L dimethyl phthalate is degraded by photoelectrocatalytic oxidation under the irradiation of an external light source and the application of biasThe light intensity of the external light source of water is 50-200 mW/cm 2 Preferably 100mW/cm 2 The bias voltage is applied to +0.2 to +0.8V, preferably +0.4V, and the photodegradation time is 0.5 to 8 hours, preferably 2 hours.
According to the invention, the essence of the photoelectrocatalysis reaction is an interface reaction process, pollutant molecules in water are adsorbed on the surface of the catalyst through a diffusion process and photoelectrocatalysis oxidation reaction occurs at the same time, and the light absorption characteristic, the surface characteristics and the accumulation amount of holes on the surface of the catalyst influence the path and the speed of the whole reaction, so that an efficient photoelectrocatalysis interface is constructed based on the factors, and the method has important significance for realizing deep removal of dimethyl phthalate in water.
Based on the method, a novel titanium mesh is selected as a substrate material, the three-dimensional mesh substrate can be folded and cut at will, the method is suitable for different complex actual environment requirements, more titanium dioxide nanorod growth sites are provided with larger specific surface area, and the adsorption capacity to pollutant molecules is greatly enhanced. The vertical growth of the one-dimensional nanorods provides a rapid channel for electron transmission, improves the separation efficiency of photogenerated carriers of the photoelectrode, and in addition, the high exposure of the {111} crystal face provides a large number of Lewis acidic sites, and has characteristic adsorption effect on Lewis basic sites in dimethyl phthalate molecules. Such {111} TiO 2 The Ti photo-anode has high-efficiency and stable photo-catalytic performance under illumination condition (the photo-current density is up to 1.8mA/cm 2 ) The highest DMP removal rate of 2mg/L can reach 100% within 2 hours, and the degradation rate is still maintained above 95% after the DMP is recycled for 4 times.
The main distinguishing/improving points of the present invention compared with the filed patent CN108911056a are:
1. titanium mesh is adopted to replace titanium plate, thus increasing the specific surface area of the electrode and in-situ growing TiO 2 Has better dispersibility and firmness. In addition, compared with the difficulty in cutting and customizing the size of the titanium plate, the titanium mesh is easy to cut and fold, so that the titanium mesh is not limited by the specification of the reactor in practical application.
2. Replacement of hydrogen with a combination of hydrochloric acid and hydrogen peroxideThe fluoric acid is used as oxidant and crystal face etchant, so that the safety coefficient is raised, and rutile TiO with {111} crystal face exposed is obtained 2 Nanorods, instead of anatase TiO with {001} crystal face exposed in the prior art 2 A nanometer microsphere. Rutile TiO 2 Has narrower band gap and wider light absorption range, and the {111} crystal face has higher surface energy (1.46J/m 2 ) The one-dimensional structure of the nanorods provides a rapid channel for electron transport, which is beneficial to realizing effective separation of photogenerated carriers.
3. The gas phase hydrothermal reaction is used to replace the conventional hydrothermal reaction, the volume of the used reaction liquid is smaller, and the cost is further reduced.
In the preparation process of the photoelectrode, the preparation conditions of each step are limited. Firstly, in the preparation process of a mixed solution required by a gas-phase hydrothermal reaction, the dosage of hydrochloric acid and hydrogen peroxide is limited, titanium dioxide nanorods with different morphologies can be obtained by different dosages of hydrochloric acid and hydrogen peroxide, moreover, the hydrochloric acid has strong corrosiveness, the titanium mesh substrate can be etched and broken due to the excessively high concentration, and the electrode material which can be used for a photoelectrocatalysis degradation experiment can not be obtained. Secondly, in the manufacturing process of the gas-phase hydrothermal reactor, the size of the annular bracket is limited. The main function of the circular support is to support the titanium mesh substrate, so that the titanium mesh substrate is flatly paved above the support and can be fully contacted with solution vapor in the reaction process, therefore, the circular support needs to have a certain wall thickness, and meanwhile, the circular support also has a proper height to ensure that the reaction stably occurs. Finally, at {111} TiO 2 In the preparation process of the Ti photoelectrode, the time of the gas phase hydrothermal reaction is limited, and the reaction time can influence the size and the growth direction of the nanorods. The reaction time is too short, the diameter of the nano rods is small, the distribution is sparse, the direction is disordered, the size of the nano rods is too large due to the too long reaction time, the connection between the rods occurs, and the photo-generated electron transmission is affected. Thus, the range of gas phase hydrothermal reaction times is defined during the preparation process, wherein 5h is the optimal reaction time.
Compared with the prior art, the invention has the following advantages:
(1) The preparation of the invention{111} TiO with high exposure of {111} crystal planes 2 The Ti high-efficiency photoelectrode adopts a titanium mesh as an electrode substrate material, and the three-dimensional mesh structure of the Ti high-efficiency photoelectrode increases the specific surface area of the electrode, thereby being beneficial to enhancing the adsorption of pollutants; the titanium mesh substrate is soft in material, easy to fold and cut, and can be cut into different sizes according to the needs, so that the titanium mesh substrate is suitable for the needs of various reactors in practical application.
(2) The titanium net is simultaneously used as a titanium source, and {111} TiO is obtained by direct in-situ growth 2 The nanorod structure solves the problems of poor firmness, easy stripping and low recycling rate of the load type electrode, and enhances the stability of the electrode.
(3) One-dimensional TiO 2 The nanorod-like structure provides a fast channel for electron transport, helps to separate photon-generated carriers, and has a {111} crystal plane exposed at the top of 1.46J/m 2 The high-activity crystal face with surface energy has good photoelectrocatalytic oxidation activity.
(4) The surface of the {111} crystal plane has 50% of unsaturated Ti 4c 50% unsaturated Ti of (C) 5c The catalyst presents rich Lewis acidic sites and has specific adsorption effect on dimethyl phthalate presenting Lewis basicity. Therefore, the constructed high-efficiency photoelectrode of the titanium dioxide with the highly exposed {111} crystal face has a high-activity reaction interface and a specific binding effect, and the two effects are mutually cooperated, so that the high-efficiency photoelectric oxidation removal of the dimethyl terephthalate can be realized.
Drawings
FIG. 1 is {111} TiO as prepared in example 1 2 Scanning electron microscope image of Ti photoelectrode;
FIG. 2 is {111} TiO prepared in examples 1, 2 2 Ti and simple rutile type TiO 2 A comparison graph of the photoelectric properties of Ti;
FIG. 3 is {111} TiO prepared in examples 1 and 2 2 Ti and simple rutile type TiO 2 In the process of degrading the DMP by the Ti photoelectrode, a ratio of the DMP concentration to the initial concentration and a time curve graph are formed;
FIG. 4 is {111} TiO as prepared in example 1 2 Cycling performance graph of photoelectrocatalytic degradation of Ti photoelectrode with 2mg/L DMP.
FIG. 5 is a scanning electron microscope image of the materials prepared in comparative examples 1 to 3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the examples below, the titanium mesh used was 80 mesh in size, and the remainder, unless otherwise specified, was all conventional commercial materials or conventional processing techniques in the art.
Example 1
Rutile TiO 2 The preparation method of the Ti photoelectrode specifically comprises the following steps:
(1) Cutting a titanium mesh into 4.5cm multiplied by 7cm, doubling back to form a double layer along the long side, heating in a mixed solution of hydrochloric acid and water (hydrochloric acid: water volume ratio is 1:1, and the concentration of hydrochloric acid used here is 36-38%) to carry out chemical polishing, carrying out ultrasonic vibration cleaning for 3 times by using deionized water and absolute ethyl alcohol in sequence after 5min, and preserving in absolute ethyl alcohol for standby.
(2) Drying the titanium mesh subjected to chemical polishing in the step (1), calcining in an air atmosphere at a heating rate of 3 ℃/min, a calcining temperature of 700 ℃ and a calcining time of 3 hours to obtain rutile TiO 2 Ti photoelectrode.
Example 2
{111} TiO with highly exposed {111} crystal face 2 The preparation method of the Ti photoelectrode specifically comprises the following steps:
(1) Cutting a titanium mesh into 4.5cm multiplied by 7cm, folding the mesh into double layers along the long sides, performing chemical polishing in a mixed acid solution containing nitric acid, hydrofluoric acid and water (nitric acid: hydrofluoric acid: water volume ratio is 5:1:25), taking out the mesh after 30 seconds, sequentially performing ultrasonic vibration cleaning with deionized water and absolute ethyl alcohol for 3 times, and finally preserving the mesh in absolute ethyl alcohol for later use.
(2) Mixing 1.9mL of hydrochloric acid (36-38% by mass fraction) and 450 mu L of hydrogen peroxide (30% by mass fraction) with 7.65mL of deionized water, uniformly stirring, transferring into a 150mL high-pressure reaction kettle liner, placing into a self-made circular polytetrafluoroethylene bracket, spreading the double-layer titanium mesh subjected to chemical polishing treatment in the step (1) above the bracket, keeping the distance from the liquid level of the reaction liquid at 6.0cm, sealing, and performing hydrothermal reaction for 5h at 200 ℃.
(3) After the reaction in the step (2) is finished, naturally cooling the reaction kettle to room temperature, taking out the photoelectrode material after the reaction, washing the photoelectrode material with deionized water, drying the photoelectrode material at 80 ℃ for 4 hours, calcining the photoelectrode material in an air atmosphere, wherein the temperature rising rate is 3 ℃/min, the calcining temperature is 450 ℃, and the calcining time is 2 hours, thus obtaining {111} TiO 2 Ti photoelectrode.
Characterization of electrode morphology using field emission scanning electron microscopy (Hitachis-4800), see FIG. 1, FIG. 1 showing TiO 2 The morphology is a nano rod-shaped structure with the surface of the titanium mesh being uniformly distributed, the diameter of a single nano rod is about 300-500 nm, and {111} TiO is prepared 2 The exposure ratio of the {111} crystal face at the top end of the Ti photoelectrode is close to 100%.
Examples 3 to 4
Compared to example 2, the vast majority are identical, except in this example: in the specific process of the titanium mesh polishing treatment, the volume ratio of nitric acid, hydrofluoric acid and water which form the polishing solution is 5:1:20 and 5:1:30 respectively.
Examples 5 to 6
Compared to example 2, the vast majority are identical, except in this example: in the composition of the gas phase hydrothermal reaction mixed solution, the volume ratio of hydrochloric acid to hydrogen peroxide to water is 4:1:17 and 5:1:17 respectively.
Example 7
Compared to example 2, the vast majority are identical, except in this example: the metallic titanium mesh was cut to a size of 3.5cm by 5 cm.
Example 8
Compared to example 2, the vast majority are identical, except in this example: the gas phase hydrothermal reaction time is respectively 4h and 6h, and the obtained electrodes are respectively marked as {111} TiO 2 Ti-4h and {111} TiO 2 /Ti-6h。
Example 9
By using a solidRutile TiO prepared in example 1 2 Ti and {111} TiO prepared in example 2 2 The Ti photoelectrode performs photoelectrocatalytic oxidation performance research, and comprises the following specific steps:
photoelectrocatalysis performance test was performed in a square quartz reaction cell with electrolyte solution of 0.1mol/L Na 2 SO 4 The solution adopts a three-electrode system, and TiO is adopted respectively 2 Ti and {111} TiO 2 Ti is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, a Chenhua CHI660C electrochemical workstation is used for testing a linear scanning voltammogram curve, a Mort-Schottky curve, an i-t curve and an alternating current impedance spectrum, the model of light source used in the experimental process is HAYSHI 150W LA-410UV-3, and the distance between the light source and the working electrode is 1cm. The test results are shown in FIG. 2, and the results show that {111} TiO 2 The photoresponse property of the Ti electrode is better than that of TiO 2 The photo current density of Ti can reach 1.8mA/cm 2 Is TiO 2 3 times of Ti, the impedance value is about 350 omega, compared with TiO 2 Reduced by about 3/4, calculated carrier concentration was 2.98X10 21 cm -3 Compared with TiO 2 The Ti is improved by 18.5 times.
Example 10
Compared to example 9, the vast majority are identical, except that in this example: the working electrode is replaced by {111} TiO 2 And (3) carrying out a photoelectrocatalysis performance test for Ti-4 h. The test result shows that the electrode has better visible light response performance under the illumination condition, and the photocurrent density can reach 1.3mA/cm 2 Impedance is about 680 Ω, carrier concentration is 2.49×10 21 cm -3 。
Example 11
Compared to example 9, the vast majority are identical, except that in this example: the working electrode is replaced by {111} TiO 2 And (3) carrying out a photoelectrocatalysis performance test after Ti-6 h. The test result shows that the electrode has better visible light response performance under the illumination condition, and the photocurrent density can reach 0.56mA/cm 2 Impedance is about 1000 omega, carrier concentration is 3.71×10 20 cm -3 。
Example 12
The rutile TiO prepared in example 1 was used 2 Ti and {111} TiO prepared in example 2 2 The Ti photoelectrode is used for degrading the wastewater containing the DMP, and the specific implementation steps are as follows:
experiments of photoelectrocatalysis degradation of DMP wastewater are carried out in a square quartz reaction tank, and electrolyte solution is 0.1 mol.L -1 The sodium sulfate solution was added to DMP to prepare a simulated wastewater at a concentration of 2mg/L, with a volume of 45mL. Adopts a three-electrode degradation system, adopts {111} TiO 2 Ti or TiO 2 The Ti electrode is a working electrode, the platinum sheet is a counter electrode, the saturated calomel electrode is a reference electrode, the distance between the working electrode and the counter electrode is 1cm, and the effective photoelectrode area is 3.5X4.5 cm 2 . The light source is a 300W xenon lamp, and the illumination intensity is 100mW/cm 2 Applying bias voltage +0.4V (relative to saturated calomel electrode), sampling every 10-30 min, degrading for 2h, filtering the sample with 0.45 μm filter head, and measuring DMP concentration by Agilent 1260 high performance liquid chromatography, wherein the specific degradation result is shown in figure 3. In FIG. 3, a represents TiO 2 Ti and {111} TiO 2 And b represents a first-order dynamic curve corresponding to the photoelectrocatalysis degradation process.
The test results in FIG. 3a show that {111} TiO 2 The Ti photoelectrode successfully realizes the high-efficiency photoelectrocatalytic oxidative degradation of the wastewater containing the DMP. After degradation for 2h, tiO 2 The removal rate of the Ti photoelectrode for the photoelectric catalytic degradation of the DMP reaches 29.8 percent, {111} TiO 2 The removal rate of the Ti photoelectrode for the photoelectrocatalytic degradation of the DMP reaches 100 percent. The high-exposure DMP molecular sieve shows that a large number of Lewis acidic sites distributed on a {111} crystal face can specifically identify DMP molecules containing Lewis basic sites, and finally high-efficiency removal of DMP pollutants in water is realized.
FIG. 3b shows that DMP-containing wastewater is treated with TiO 2 Ti and {111} TiO 2 The removal process on the Ti photoelectrode accords with the quasi-first-order reaction kinetics.
Example 13
Use of {111} TiO prepared in example 2 2 DMP simulated wastewater was degraded by Ti photoelectrode cycle, compared with example 12Largely identical except in this embodiment: {111} TiO 2 After the Ti photoelectrode degrades DMP wastewater for 2 hours, the electrode material is washed clean by deionized water, and the degradation process is repeated after drying, so that the electrode is recycled four times.
The degradation results are shown in FIG. 4, {111} TiO 2 The Ti photoelectrode has good stability, the degradation efficiency of DMP is not obviously changed in the process of repeated cyclic use, and the degradation rate is still maintained above 95% after four times of degradation. The results of the cyclic degradation experiments show that the titanium dioxide nanorod grown in situ on the titanium mesh substrate has higher structural firmness, is not easy to fall off in the actual degradation application process, and can realize the recovery and the reuse of the electrode.
Example 14
Compared to example 12, the vast majority are identical, except in this example: the concentration of DMP is changed to 1mg/L, and a photoelectrocatalytic degradation experiment is carried out.
Comparative example 1
In comparison with example 2, the same is mostly true, but instead the titanium mesh after chemical polishing is directly placed in a mixed solution for conventional hydrothermal reaction. As shown in fig. 5 (a), the titanium mesh breaks after the hydrothermal reaction.
Comparative example 2
Most of the same as in example 2 except that hydrochloric acid was changed to an equimolar amount of hydrofluoric acid. As shown in FIG. 5 (b), after the gas phase hydrothermal reaction, the titanium mesh is corroded and crushed.
Comparative example 3
Most of the same was made as in example 2, except that the addition of hydrogen peroxide was omitted. As shown in fig. 5 (c) and (d), after the gas-phase hydrothermal reaction, the titanium mesh structure is perfect, the nanorod layer grows on the surface, but the nanorod structure is disordered, and the {111} crystal face exposure proportion is low.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (13)
1. A method for preparing a {111} crystal face high-exposure titanium dioxide high-efficiency photoelectrode is characterized in that a titanium mesh is taken for chemical polishing, then is placed above a mixed reaction solution consisting of hydrochloric acid, hydrogen peroxide and water for gas phase hydrothermal reaction, and a sample obtained after the reaction is cleaned, dried and then calcined, so that a target product is obtained;
the volume ratio of hydrochloric acid, hydrogen peroxide and water in the mixed reaction solution is 4:1:17-5:1:17, the mass fraction of the hydrochloric acid is 36-38%, and the mass fraction of the hydrogen peroxide is 30%;
the temperature of the gas phase hydrothermal reaction is 180-220 ℃ and the time is 2-12 h;
fixing a titanium net at a position 5.5-6.5 cm above the liquid level of the mixed solution by using a polytetrafluoroethylene bracket;
calcining is carried out in air atmosphere, the calcining temperature is 400-550 ℃, and the calcining time is 1-3 h;
the temperature rising rate in the calcination process is 1-5 ℃/min.
2. The method for preparing the {111} crystal face highly exposed titanium dioxide high-efficiency photoelectrode according to claim 1, wherein the chemical polishing process is specifically as follows: and (3) placing the titanium mesh in a mixed acid solution containing nitric acid, hydrofluoric acid and water for treatment, wherein the volume ratio of the nitric acid to the hydrofluoric acid to the water is 5:1:20-5:1:50.
3. The method for preparing a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode according to claim 2, wherein the volume ratio of nitric acid, hydrofluoric acid and water is 5:1:25.
4. The method for preparing a {111} crystal face highly exposed titanium dioxide efficient photoelectrode according to claim 1, wherein the volume ratio of hydrochloric acid, hydrogen peroxide and water in the mixed reaction solution is 4.2:1:17.
5. The method for producing a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode according to claim 1, wherein the temperature of the vapor phase hydrothermal reaction is 200 ℃ for 5 hours.
6. The method for preparing a {111} crystal face highly exposed titanium dioxide high-efficiency photoelectrode according to claim 1, wherein a polytetrafluoroethylene support is used to fix a titanium mesh 6.0cm above the liquid level of the mixed solution.
7. The method for producing a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode according to claim 1, wherein the calcination temperature is 450 ℃, and the calcination time is 2 hours.
8. The method for preparing a {111} crystal face highly exposed titanium dioxide efficient photoelectrode according to claim 1, wherein a temperature rising rate in the calcination process is 3 ℃/min.
9. A {111} crystal face highly exposed titanium dioxide high-efficiency photoelectrode prepared by the preparation method according to any one of claims 1 to 8.
10. The use of a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode as claimed in claim 9 for photoelectrocatalytic oxidation of dimethyl phthalate contaminants in water.
11. The use of a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode as claimed in claim 10, wherein a three electrode system is used, respectively as {111} TiO 2 Ti photoelectrode, platinum sheet, saturated calomel electrode as working electrode, counter electrode and reference electrode, sodium sulfate deionized water solution as electrolyte, and photoelectrocatalytic oxidation reduction under the irradiation of external light source and the application of biasAnd (3) decomposing waste water containing dimethyl phthalate.
12. The use of a {111} crystal face highly exposed titanium dioxide high efficiency photoelectrode according to claim 11, wherein the concentration of the sodium sulfate deionized water solution used is 0.1mol/L;
the concentration of the waste water containing dimethyl phthalate is 2mg/L, and the light intensity of an external light source is 50-200 mW/cm 2 The bias voltage is applied to be +0.2 to +0.8V, and the photodegradation time is 0.5 to 8 hours.
13. The use of a highly exposed titanium dioxide high efficiency photoelectrode according to claim 12 wherein the applied light source has an intensity of 100mW/cm 2 The bias voltage is applied to be +0.4V, and the photodegradation time is 2h.
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| CN108249478B (en) * | 2018-01-30 | 2020-03-17 | 成都大学 | Preparation method of rutile phase titanium dioxide with micro-flower structure |
| CN108911056B (en) * | 2018-03-23 | 2021-06-04 | 同济大学 | Preparation and application of {001} crystal face controllable exposure titanium dioxide photoelectrode |
| CN111647880B (en) * | 2019-03-04 | 2022-09-02 | 中国科学院宁波材料技术与工程研究所 | Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate |
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