CN113189174B - Titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property and preparation and application thereof - Google Patents
Titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a titanium dioxide photoelectrode with three-dimensional crystal plane junction property, and preparation and application thereof, wherein the titanium dioxide photoelectrode takes a titanium mesh as a titanium source, hydrochloric acid as a morphology control agent, hydrogen peroxide as an oxidant, and one-dimensional vertical rutile TiO with exposed top {111} crystal plane grows in situ on a titanium mesh substrate by a gas-phase hydrothermal method 2 A nanorod; then the {101}, 111} nano-sheets are grown outside the nano-rod through secondary hydrothermal reaction to form a three-dimensional crystal face Junction (FH), and the growth density and the exposure proportion of the nano-sheets are optimized through adjusting the hydrothermal reaction time and the solvent proportion, so that the prepared FH- {111} TiO is prepared 2 The Ti photoelectrode can be applied to the deep removal of bisphenol A (BPA) wastewater. Compared with the prior art, the titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property ({ 111}/{101}, {111}/{110}, {110}/{101 }) has high charge separation capability and high-efficiency photoelectrocatalytic oxidation capability, and shows 100% removal of bisphenol A in 20-60 min.
Description
Technical Field
The invention belongs to the technical field of photoelectrocatalysis, and relates to a titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property, and preparation and application thereof.
Background
Bisphenol a (BPA) is a semi-persistent environmental endocrine disrupter, exhibiting estrogen-like effects, although smaller doses can cause a range of hazards such as reproductive toxicity, neurotoxicity, diabetes, carcinogenesis, etc. BPA is used primarily in the production of epoxy and polycarbonate plastics and is therefore commonly found in food can liners, polycarbonate plastics, flame retardants, thermal receipts, epoxy resins and medical devices. In China, the BPA is large in usage amount, and BPA is detected in water discharged from a plurality of urban river channels, sewage plants and the like,in particular, the content of BPA detected in the wastewater discharged from paper mill, fine chemical plant, etc. is higher than the specified limit value of national standard (BPA 15.72ng L -1 ) Is hundreds of times greater than tens of times. BPA in nature is damaged by living beings after entering the living beings through the actions of biological concentration, biological accumulation and biological amplification, so that irreversible damage is caused to the living beings, and therefore, great importance is paid to BPA pollution in countries around the world, for example, the dosage of BPA is regulated in food contact material detection standards (GB 4806-2016) in China. Therefore, the efficient removal of BPA in water is a hot spot subject in the current environmental water treatment field.
In the last decades, titanium dioxide (TiO 2 ) Because of the advantages of chemical stability, environmental friendliness and avoidance of photo-corrosion, the polymer has wide application prospects in the fields of photocatalysis, photoelectrocatalysis, solar cells and the like. Compared with anatase titanium dioxide with wide application, rutile titanium dioxide is the most thermodynamically stable crystal form, and has a narrower band gap at room temperature, about 3.0eV, so that the photoresponse range can be widened to the visible light region, but the application capability of the rutile titanium dioxide is limited due to the fast recombination rate of photo-generated electron hole pairs.
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 photoelectrocatalytic oxidative degradation of dimethyl phthalate wastewater, and has higher photoelectrocatalytic degradation performance, but the flat electrode prepared by taking a titanium plate as a substrate has less exposure of growth sites and grows TiO (titanium dioxide) 2 The flower-shaped microspheres are stacked layer by layer, which is not beneficial to the selective spatial separation of the photogenerated carriers and is easy to fall off; in addition, the titanium plate substrate is difficult to cut and is limited in practical application.
Disclosure of Invention
The invention aims to provide a titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property, and preparation and application thereof, which can obviously promote separation and transfer of photo-generated charges and effectively realize degradation and removal of bisphenol A in water.
The aim of the invention can be achieved by the following technical scheme:
on one hand, the invention provides a preparation method of a titanium dioxide photoelectrode with three-dimensional crystal face crystallization property, which comprises the steps of firstly using a titanium mesh as a titanium source, hydrochloric acid as a morphology control agent, hydrogen peroxide as an oxidant, and growing one-dimensional vertical rutile TiO with exposed top {111} crystal faces on a titanium mesh substrate in situ by a gas-phase hydrothermal method 2 A nanorod; then the {101}, 111} nano-sheets are grown outside the nano-rod through secondary hydrothermal reaction to form a three-dimensional crystal face structure, and the FH- {111} TiO with three-dimensional crystal face structure property is obtained 2 And (3) Ti photoelectrode, namely the target product. Specifically, the preparation process comprises the following steps:
(1) Placing a titanium mesh above a mixed solution composed of hydrochloric acid, hydrogen peroxide and water for one-time gas-phase hydrothermal reaction to obtain an intermediate sample (which grows in situ on a titanium mesh substrate a one-dimensional upright rutile TiO with exposed top {111} crystal face) 2 A nanorod);
(2) Placing the intermediate sample in a mixed solution prepared from hydrochloric acid, titanium trichloride and deionized water, continuing the secondary hydrothermal reaction, washing the obtained product (growing {101}, {111} nanosheets outside the nanorods to form a three-dimensional crystal face structure), drying and calcining to obtain the target product, namely FH- {111} TiO with the three-dimensional crystal face structure property 2 Ti photoelectrode.
Further, in the step (1), the titanium mesh is first subjected to chemical polishing, and the chemical polishing process is preferably specifically: nitric acid (the concentration is more than or equal to 99.0 percent), hydrofluoric acid (more than or equal to 38 weight percent) and water in a volume ratio of 5:1:25, treating in the polishing solution prepared by the method.
Further, in the step (1), the volume ratio of the hydrochloric acid to the hydrogen peroxide to the water is 4.2:1:17 to 5.3:1:17, preferably 4.8:1:17; the mass fraction of the hydrochloric acid is 36-38%, and the mass fraction of the hydrogen peroxide is 30%.
Further, in the step (1), the temperature of the primary gas phase hydrothermal reaction is 180 to 220 ℃, preferably 200 ℃, and the time is 2 to 12 hours, preferably 5 hours.
Further, in the step (2), the titanium trichloride is added in the form of a titanium trichloride solution, and the volume ratio of the added hydrochloric acid to the titanium trichloride solution to the deionized water is 1:0.2:120-1:2.4:120, wherein the mass fraction of the titanium trichloride solution is 15-20%.
Further, in the step (2), the temperature of the secondary hydrothermal reaction is 80 ℃, and the time is 2-5 hours, preferably 4 hours.
Further, in the step (2), the calcination is performed under an air atmosphere at 400 to 550 ℃, preferably 450 ℃, for 1 to 3 hours, preferably 2 hours.
On the other hand, the invention also provides a titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property, which is prepared by adopting the preparation method, and the TiO of the titanium dioxide photoelectrode 2 The three-dimensional structure grows densely along the grid structure of the titanium mesh. Meanwhile, the diameter of the nano rod is between 150 and 250nm, and the length is about 2.3 mu m.
In still another aspect, the invention also provides an application of the titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property in removing bisphenol A pollutants in water by photoelectrocatalytic oxidation.
Further, in specific application, a three-electrode system is adopted, a titanium dioxide photoelectrode, a platinum sheet and a saturated calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, a sodium sulfate deionized water solution is used as an electrolyte, and wastewater containing bisphenol A is degraded by photoelectrocatalytic oxidation under the irradiation of an external light source and the application of bias.
Further, the concentration of the deionized water solution of sodium sulfate is 0.1mol/L;
the concentration of the wastewater containing bisphenol A is 2-10 mg/L, and the light intensity of an external light source is 50-200 mW/cm 2 Preferably 100mW/cm 2 The distance between the working electrode and the light source is 5-20 cm, the bias voltage is applied to be +0.2 to +1.0V, preferably +0.4V, and the photodegradation time is 0.5-4 h, preferably 1h.
According to the invention, the essence of the photoelectrocatalysis reaction is that the interface reaction process is the photoelectrocatalysis oxidation reaction occurs simultaneously when pollutant molecules in water are adsorbed on the surface of the catalyst after being diffused, and the light absorption efficiency, the surface property and the charge separation efficiency of the catalyst influence the path and the speed of the whole reaction, so that the construction of the high-efficiency photoelectrocatalysis interface based on the factors has important significance for realizing the deep removal of bisphenol A in water.
Based on the method, the novel titanium mesh is selected as the substrate material, the three-dimensional mesh substrate can be folded and cut at will, the method is suitable for the requirements of different reactors in practical application, and uniform titanium dioxide nanorod growth sites are provided. The vertical growth of the one-dimensional nanorods provides a rapid channel for electron transport, with highly exposed {111} faces at the top of the nanorods having high reactivity. The two-dimensional nano-sheets ({ 111}, 101 }) are grown outside the nano-rod, and the nano-rod has a high specific surface, so that the adsorption capacity for pollutant molecules is greatly enhanced. And the construction of three-dimensional crystal plane junction (111/{ 101}, { 111/{ 110}, {110}/{101 }) among {111}, {101}, 110}/{101}, is helpful to promote efficient selective spatial separation of photogenerated carriers (the highest carrier concentration reaches 3.99X10 }) 21 cm -3 The excited electron lifetime is between 23.06 and 24.27 ns). This FH- {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 0.56mA/cm 2 ) Shows 100% removal of bisphenol a in 20 to 60 min.
The photoelectrode preparation is realized by a two-step hydrothermal method, and is influenced by two factors of solvent proportion and time, so that the solvent proportion and the hydrothermal time are limited. Firstly, in the preparation of the mixed solution required for the gas-phase hydrothermal reaction, the amounts of hydrochloric acid and hydrogen peroxide and the time of the gas-phase hydrothermal reaction are limited, cl - The titanium dioxide nano-rods are adsorbed on the {110} surface, so that the growth of the {111} surface is facilitated, titanium dioxide nano-rods with different morphologies can be obtained by using different amounts of hydrochloric acid and hydrogen peroxide, and the reaction time can influence the size and the growth direction of the nano-rods. Too short reaction time, small diameter of the nano rods, sparse distribution and disordered direction, too long reaction time can cause the nano rods to be too large in size, and influence the growth of the two-dimensional nano sheetsWherein 5h is the optimal reaction time. Secondly, in the secondary hydrothermal process, the solvent ratio of hydrochloric acid and titanium trichloride affects the growth density and exposure ratio of the two-dimensional nanoplatelets, so the above factors are limited. When the concentration of the titanium trichloride is low, the size and the concentration of the two-dimensional nano-sheets can be influenced, and on the other hand, the hydrothermal reaction time is long, so that the production cost is increased; the titanium trichloride has high concentration, so that the two-dimensional nano-sheet grows too densely, and exposure of {110} side surfaces and {111} top surfaces of the nano-rod is not facilitated. Finally, the time of the hydrothermal reaction in the secondary hydrothermal process is limited, the reaction time is too short, the nano sheet structure is not obvious, the nano sheet is too large in size due to the too long reaction time, the connection between rods occurs, the separation efficiency of the photon-generated carriers is reduced, and 4h is the optimal reaction time.
Based on the method, the novel titanium mesh is selected as the substrate material, and the three-dimensional mesh substrate can be folded and cut at will, so that the method is suitable for the requirements of different reactors in practical application. And the construction of three-dimensional crystal surface junctions (111/{ 101}, { 111/{ 110}, 110}/{101 }) among {111}, 101}, 110}, helps to promote efficient selective spatial separation of photogenerated carriers. This FH- {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 0.56mA/cm 2 ) Shows 100% removal of bisphenol a in 20 to 60 min.
Compared with the prior art, the invention has the following advantages:
(1) The {111} crystal face high exposure FH- {111} TiO prepared by the invention 2 The Ti high-efficiency photoelectrode adopts a titanium mesh as an electrode substrate material, the three-dimensional mesh structure provides compact titanium dioxide nanorod growth sites, the material is softer, the photoelectrode is easy to fold and cut, and the photoelectrode can be cut into different sizes according to the needs, so that the photoelectrode 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 vertical growth of the nanorod-like structure provides a fast path for electron transport, with the {111} crystal plane exposed at the top of the nanorod-like structure being 1.46J/m 2 The high-activity crystal face with surface energy has good photoelectrocatalytic oxidation activity.
(4) The two-dimensional nano-sheets ({ 111}, and {101 }) are externally grown on the nano-rod to form a three-dimensional high-level structure, so that the adsorption capacity of the nano-rod on pollutant molecules is greatly enhanced.
(5) The structure of the crystal plane junction {111}/{101}, {111}/{110}, {110}/{101} helps to promote efficient selective spatial separation of photogenerated carriers.
Therefore, the constructed titanium dioxide photoelectrode with three-dimensional crystal face junction property has a high-activity reaction interface and high-efficiency photo-generated carrier separation capability, and the two effects are mutually cooperated to realize high-efficiency photoelectric oxidation removal of bisphenol A.
Drawings
FIG. 1 is FH- {111} TiO as prepared in example 1 2 Scanning electron microscope image of Ti photoelectrode;
FIG. 2 shows FH- {111} TiO as prepared in examples 1, 2 2 Ti and {111} TiO 2 A comparison graph of the photoelectric properties of Ti;
FIG. 3 is FH- {111} TiO as prepared in example 1 2 Ti and {111} TiO 2 Fluorescence spectrogram of Ti photoelectrode and time-resolved transient fluorescence spectrogram;
FIG. 4 shows FH- {111} TiO as prepared in examples 1 and 2 2 Ti and {111} TiO 2 In the process of degrading BPA by Ti photoelectrode, a BPA concentration-initial concentration ratio and a time curve graph are formed;
FIG. 5 is a scanning electron microscope image of the photoelectrodes prepared in comparative example 1, comparative example 2 and comparative example 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
{111} 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, 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 2.2mL 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 6cm, 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.
Example 2
The preparation method of the titanium dioxide photoelectrode with the three-dimensional crystal plane junction property 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 2.2mL of hydrochloric acid (about 37% by mass fraction) and 450 mu L of hydrogen peroxide (about 30% by mass fraction) with 7.65mL of deionized water, stirring uniformly, transferring into a 150mL high-pressure reaction kettle liner, placing a self-made annular polytetrafluoroethylene bracket, spreading the double-layer titanium mesh subjected to chemical polishing treatment in the step (1) above the bracket, keeping the position 6cm away from the liquid level of the reaction liquid, sealing, and performing hydrothermal reaction for 5h at 200 ℃.
(3) And (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, and drying the photoelectrode material for later use. Adding 30mL deionized water and 250 μL hydrochloric acid (about 37% by mass) and 100 μL titanium trichloride (about 18% by mass) into 100mL polytetrafluoroethylene substrate, mixing uniformly, and adding {111} TiO prepared in step (2) 2 And (3) putting the Ti one-dimensional rutile nano rod into the reaction kettle, putting the polytetrafluoroethylene substrate into a high-pressure reaction kettle, carrying out hydrothermal reaction for 4 hours at 80 ℃, cooling to room temperature after the reaction is finished, flushing the surface with deionized water, and naturally airing.
Calcining in air atmosphere at heating rate of 3 deg.c/min and calcining temperature of 450 deg.c for 2 hr to obtain FH- {111} TiO 2 Ti photoelectrode.
Characterization of electrode morphology by field emission scanning electron microscopy (Hitachis-4800), see FIG. 1, FIG. 1 showing FH- {111} TiO 2 The Ti morphology is a three-dimensional advanced structure with evenly distributed titanium mesh surface, the diameter of a single one-dimensional upright nano rod is about 150-250 nm, the two-dimensional nano sheet branch structure outside the nano rod is neat, the growth direction is consistent, about 62nm, and the prepared FH- {111} TiO is prepared 2 The {111}, {110}, and {101} crystal planes of the Ti photoelectrode are co-exposed.
Examples 3 to 4
Compared to example 2, the vast majority are identical, except in this example: the gas phase hydrothermal reaction time is 4h and 8h 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 4.2:1:17 and 5.3:1:17 respectively.
Example 7
Compared to example 2, the vast majority are identical, except in this example: the secondary hydrothermal reaction time is 2h and 5h respectively.
Example 8
Compared to example 2, the vast majority are identical, except in this example: in the composition of the secondary hydrothermal reaction mixed solution, the volume ratio of hydrochloric acid, titanium trichloride and deionized water is 1:0.2:120 and 1:0.8:120, and the obtained electrodes are respectively marked as FH- {111} TiO 2 Ti-0.2 and FH- {111} TiO 2 /Ti-0.8。
Example 9
The {111} TiO prepared in example 1 was used 2 Ti and FH- {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 {111} TiO is respectively used for 2 Ti and FH- {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 results show that in the range of 0-1.5V vs SCE, FH- {111} TiO 2 The PEC response of the/Ti photoelectrode is significantly higher than that of {111} TiO 2 A Ti photoelectrode (FIG. 2 a). As can be seen from FIG. 2b, FH- {111} TiO 2 The photocurrent density of Ti was about 0.56mA cm -2 Is {111} TiO 2 2.9 times of Ti (about 0.19mA cm) -2 ). FIGS. 2c and 2d show the Mort-Schottky curve and the AC impedance spectrum, respectively, under illumination, and it can be seen that FH- {111} TiO 2 The impedance value of/Ti is about 166. Omega. Compared with {111} TiO 2 Reduced by about 0.26, the calculated carrier concentration was 3.99X10 21 cm -3 Compared with {111} TiO 2 The Ti is improved by 16.5 times.
Example 10
As in example 9The ratio is largely the same except in this example: changing working electrode to FH- {111} TiO 2 and/Ti-0.2, and performing photoelectrocatalysis performance test. The test result shows that the electrode has better photoresponsivity and photocurrent density reaching 0.27mA/cm under the illumination condition 2 Impedance is about 530 omega, carrier concentration is 1.54×10 21 cm -3 。
Example 11
Compared to example 9, the vast majority are identical, except that in this example: changing working electrode to FH- {111} TiO 2 and/Ti-0.8, and performing photoelectrocatalysis performance test. The test result shows that the electrode has better photoresponsivity and photocurrent density reaching 0.46mA/cm under the illumination condition 2 Impedance is about 286 omega, carrier concentration is 1.02X10 21 cm -3 。
Example 12
The {111} TiO prepared in example 1 was used 2 Ti and FH- {111} TiO prepared in example 2 2 The Ti photoelectrode is subjected to fluorescence spectrum and time-resolved transient fluorescence spectrum tests, see FIG. 3, which shows that the construction of the three-dimensional crystal face junction remarkably improves the separation capability of photo-generated charges and prolongs the service life of excited electrons (FH- {111} TiO) 2 /Ti：24.27ns；{111}TiO 2 /Ti：22.89ns)。
Example 13
The {111} TiO prepared in example 1 was used 2 Ti and FH- {111} TiO prepared in example 2 2 The method for degrading the wastewater containing BPA by the Ti photoelectrode comprises the following specific implementation steps:
experiments of photoelectrocatalysis degradation of BPA wastewater are carried out in a square quartz reaction tank, and electrolyte solution is 0.1 mol.L -1 The sodium sulfate solution is added with BPA to prepare simulated wastewater with the concentration of 5mg/L and the volume of 45mL. Adopts a three-electrode degradation system, adopts FH- {111} TiO 2 /Ti or {111} 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 +0.4VRelative to a saturated calomel electrode), sampling is carried out every 5-10 min, the degradation time is 1h, the concentration of BPA in the sample is measured by adopting Agilent 1260 high performance liquid chromatography, and the specific degradation result is shown in figure 4. In FIG. 4, a represents FH- {111} TiO 2 Ti and {111} TiO 2 And b represents a first-order dynamic curve corresponding to the photoelectrocatalysis degradation process.
FIG. 4a shows that FH- {111} TiO 2 The Ti photoelectrode successfully realizes the high-efficiency photoelectrocatalytic oxidative degradation of the wastewater containing BPA. After degradation for 1h, {111} TiO 2 The photoelectrocatalytic degradation removal rate of the Ti photoelectrode for BPA reaches 94.95 percent, while the FH- {111} TiO 2 The photoelectrocatalytic degradation removal rate of the Ti photoelectrode for BPA reaches 100% in only 20 min. Indicating the FH- {111} TiO with controllable co-exposure of {111}, {101}, {110} crystal faces 2 The Ti photoelectrode has high photogenerated carrier separation efficiency, and finally realizes the efficient removal of BPA pollutants in water.
FIG. 4b shows that the BPA-containing wastewater is at FH- {111} TiO 2 Ti and {111} TiO 2 The removal process on the Ti photoelectrode accords with the quasi-first-order reaction kinetics. Use of {111} TiO prepared in example 2 2 Ti photoelectrode cycle degradation BPA simulated wastewater, compared to example 12, is largely identical except in this example: {111} TiO 2 After degrading BPA wastewater for 2 hours by using a Ti photoelectrode, washing the electrode material with deionized water, drying, repeating the degradation process, and recycling the electrode four times.
Examples 14 to 15
Compared to example 13, the vast majority are identical, except in this example: the concentration of BPA is changed to 2mg/L and 10mg/L, and a photoelectrocatalysis degradation experiment is carried out.
Comparative example 1
Compared with example 2, most of the steps are the same, except that step (2) is omitted, namely, the titanium mesh after chemical polishing is directly put into a mixed solution of hydrochloric acid, titanium trichloride and water to carry out hydrothermal reaction, as shown in fig. 5a, the nano particles directly growing on the titanium mesh are prepared.
Comparative example 2
Most of the same as in example 2 except that the amount of titanium trichloride added in step (3) was adjusted to 30. Mu.L, as shown in FIG. 5b, no significant secondary nanoplatelets grew outside the nanorods.
Comparative example 3
Most of the same as in example 2 except that the amount of titanium trichloride added in step (3) was adjusted to 700. Mu.L, a large number of nano-sheets were grown outside the nano-rod, and the nano-rods were stacked layer by layer, interconnected, and damaged the one-dimensional upright structure of the nano-rod substrate as shown in FIG. 5 c.
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 (5)
1. The preparation method of the titanium dioxide photoelectrode with the three-dimensional crystal plane junction property is characterized by comprising the following steps of:
(1) Placing a titanium mesh above a mixed solution composed of hydrochloric acid, hydrogen peroxide and water for a primary gas-phase hydrothermal reaction to obtain an intermediate sample;
(2) Placing the intermediate sample into a mixed solution prepared from hydrochloric acid, titanium trichloride and deionized water, continuing the secondary hydrothermal reaction, and cleaning, drying and calcining the obtained product to obtain a target product;
in the step (1), the volume ratio of hydrochloric acid to hydrogen peroxide to water is 4.2:1:17 to 5.3:1:17; the mass fraction of the hydrochloric acid is 36-38%, and the mass fraction of the hydrogen peroxide is 30%;
in the step (1), the temperature of the primary gas phase hydrothermal reaction is 180-220 ℃ and the time is 2-12 h;
in the step (2), titanium trichloride is added in the form of titanium trichloride solution, and the volume ratio of the added hydrochloric acid to the titanium trichloride solution to deionized water is 1:0.2:120-1:2.4:120, wherein the mass fraction of the titanium trichloride solution is 15-20%;
in the step (2), the temperature of the secondary hydrothermal reaction is 80 ℃ and the time is 2-5h;
in the step (2), the calcination is performed in an air atmosphere, the calcination temperature is 400-550 ℃, and the calcination time is 1-3 h.
2. A titanium dioxide photoelectrode having three-dimensional crystal plane junction properties, which is prepared by the preparation method as claimed in claim 1, characterized in that the TiO of the titanium dioxide photoelectrode is 2 The three-dimensional structure grows densely along the grid structure of the titanium mesh.
3. The use of a titanium dioxide photoelectrode having three dimensional crystal plane properties as claimed in claim 2 for the photoelectrode of bisphenol a contaminants in water by photoelectrocatalytic oxidation.
4. The application of the titanium dioxide photoelectrode with three-dimensional crystal plane crystallization property according to claim 3, wherein in the specific application, a three-electrode system is adopted, the titanium dioxide photoelectrode, a platinum sheet and a saturated calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, a sodium sulfate deionized water solution is used as an electrolyte, and the wastewater containing bisphenol A is subjected to photoelectrocatalytic oxidation degradation under the irradiation of an external light source and the application of bias voltage.
5. The use of a titanium dioxide photoelectrode having three-dimensional crystal plane properties according to claim 4, wherein the concentration of the deionized water solution of sodium sulfate used is 0.1mol/L;
the concentration of the wastewater containing bisphenol A is 2-10 mg/L, and the light intensity of an external light source is 50-200 mW/cm 2 The distance between the working electrode and the light source is 5-20 cm, the applied bias voltage is +0.2 to +1.0V, and the photodegradation time is 0.5-4 h.
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