CN112892514B - Synthesis method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {136} surface - Google Patents
Synthesis method of anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {136} surface Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims description 9
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- 239000002253 acid Substances 0.000 claims description 11
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- 239000002245 particle Substances 0.000 claims description 8
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- 238000001035 drying Methods 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 4
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- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- -1 light emission Substances 0.000 description 2
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- 150000003608 titanium Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/33—
-
- B01J35/39—
Abstract
The invention discloses a preparation method of an anatase titanium oxide polyhedral catalyst with exposed high-index {136} faces. The method synthesizes the regular polyhedral TiO with specific morphology firstly 2 As a mother crystal, then, an etching experiment is performed by using organic/inorganic acids with different concentrations as chemical etchants, and a high-index {136} plane is introduced into the crystal in the secondary modulation of the morphology. The pH is controlled, the etching time is changed, the exposure proportion of the {136} surface can be regulated and controlled, and the obtained crystal has uniform morphology and excellent photocatalytic performance and photoelectrochemical performance.
Description
Technical Field
The invention relates to preparation of an anatase titanium oxide catalyst, in particular to a preparation method of a titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {136} faces.
Background
Among inorganic materials, anatase titanium oxide is an important semiconductor material, tiO 2 Because of its chemical and biological inertness, cost effectiveness, and strong oxidizing power of photo-generated holes, attention has been paid to wide application in catalysis, photovoltaic cells, self-cleaning devices, sensors, lithium ion battery materials, light emission, water decomposition, paints, and the like. How to further improve the performance and the utilization efficiency of the titanium dioxide material is a key problem in the field. The activity of the catalyst can be achieved by adjusting its size, morphology, crystal face ratio, exposing new crystal faces, i.e. by controlling the atomic arrangement structure of the surface (see literature: angel. Chem.2011,123,1361-1365; adv. Funct. Mater.2011,21, 3554-3563).
Basic research on single crystal model catalysts indicates that the high index surface contains a structure of high density of step atoms, kink atoms, surface dangling bonds, and the like, and has superior performance to the low index surface (see, literature: nature,1975,258,580-583). Thus, the preparation of nanocrystals that primarily expose high index facets is an important route to the preparation of nanocatalysts with high activity and stability. For example, tiO which mainly exposes {105} high energy surface is synthesized by hydrothermal method in the subject group such as Huadong university of Summit 2 Octahedron (see: angew. Chem.2010, 123, 3848-3852). However, nanocrystals with exposed high index facets tend to be difficult to produce because they tend to have high surface energies, resulting in a fast growth rate during crystal growth that tends to disappear.
The growth of the high-index surface is closely related to the preparation conditions thereof, and since the preparation of the high-index surface is thermodynamically unfavorable, the synthesis of the high-index surface is generally severe in conditions and difficult to scale up. So far, researches on crystal face regulation and application of titanium oxide at home and abroad have been reported, for example, truncated octahedron exposing {001} crystal face, octahedron exposing {101} crystal face mainly, cube exposing {100} face, nano rod exposing {010} face and other titanium oxide polyhedrons are reported successively.
The most common strategy for preparing crystals with exposed high-index surfaces is to use a capping agent to selectively adsorb the capping agent on the crystal surface to change the surface energy of crystal faces and realize the modulation of the growth rate of the capping agent, so that crystals with exposed high-index surfaces are obtained, but the capping ions which are mature and serve as capping agents to regulate the high-energy surfaces are mostly F - And all the crystal planes {001} are regulated and controlled. And some ligand ions are difficult to completely remove, and the activity of crystal faces is disturbed.
The control of growth conditions can realize the modulation of crystal growth dynamics, and can also realize selective high-energy surface, however, the growth process of the crystal is sensitive to conditions, and any change of the growth conditions of the crystal can lead to the change of the morphology of a product, which leads to the fact that the synthesis in a laboratory is difficult to realize in a large scale.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an anatase titania polyhedral nano/micro photocatalyst exposing a high index {136} face.
The technical scheme of the invention is as follows:
the preparation method of the anatase titanium oxide polyhedral nano/micron photocatalyst with the exposed high-index {136} surface comprises the following steps:
(1) Synthesizing polyhedral mother crystals, namely dissolving titanium salt and acid in distilled water according to the molar ratio of 0.02-300, treating the solution in an ultrasonic instrument for 10-20 min, transferring the solution into a reactor, reacting for 2-48 h at 50-400 ℃, cooling to room temperature, pouring out supernatant, washing for 3-5 times by absolute ethyl alcohol, drying for 8-24 h in an oven, obtaining solid which is titanium oxide polyhedral particles exposing {101} and {001} crystal faces, and calcining the dried sample at 300-1000 ℃ for 1-48 h to obtain titanium oxide polyhedral mother crystals; (2) Etching to obtain a high-index surface, placing the titanium oxide polyhedral mother crystal obtained in the step (1) into acid with the pH value of 0.1-0.9, carrying out ultrasonic treatment for 10-20 min, transferring the solution into a reactor, etching for 1-60 h at the temperature of 10-250 ℃, cooling to room temperature, washing 3-5 times by using absolute ethyl alcohol, centrifuging to collect solid, and drying in an oven for 8-24 h to obtain solid, namely titanium oxide polyhedral particles with exposed {136} crystal faces ({ 101} and {001} crystal faces still exist in the obtained catalyst, but the high-index {136} face is a newly exposed crystal face, and a higher proportion can be achieved). Further, in the step (1), the titanium source is one of tetrabutyl titanate, titanium sulfate, titanyl sulfate or titanium fluoride, and the titanium salt has the characteristics of easy acquisition and reasonable cost.
Further, in the step (1), the acid is one of hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, citric acid and ascorbic acid, and the acid has the characteristics of easy availability and reasonable cost.
Further, in the step (2), the acid is one of hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, citric acid and ascorbic acid, and the acid has the characteristics of easy availability and reasonable cost.
Further, in the step (1) and the step (2), the drying temperature is 60-80 ℃.
The anatase titanium oxide polyhedral nano/micron photocatalyst with the exposed high-index surface obtained by the preparation method has excellent photodegradation performance and photoelectrochemical performance.
The invention relates to a method for preparing a high-index {136} surface nano-particle by using different acids as chemical etchants, etching titanium oxide crystals with different morphologies synthesized in advance by controlling pH, and secondarily modifying the morphology of the titanium oxide crystals. The morphology of the resulting nanoparticles is also different due to the different etching times. The high-index {136} plane is a specific high-index crystal plane of the titanium oxide crystal. So far, no report has been made. On the one hand, since the newly exposed {136} face has a small surface atomic density, it has a large photocurrent intensity; on the other hand. The special structure of the crystal face can be used as a model catalyst, and provides a beneficial guide for the development of the titanium oxide-based high-efficiency catalyst.
The invention has the beneficial effects that:
(1) The invention combines two strategies of top-down and bottom-up for regulating the morphology of titanium oxide, and controls the crystal growth based on the thermodynamically favorable direction of the two strategies, thus obtaining the anatase titanium oxide crystal with exposed {136} surface, and the obtained crystal has uniform morphology.
(2) The titanium oxide polyhedron obtained by the invention mainly comprises crystal faces with indexes of {101}, {001} and {136} series, and the proportion among the three crystal faces is adjustable, so that a good model catalyst is provided for researching the surface heterojunction.
(3) The preparation method of the invention is simple.
(4) The crystal face proportion of the titanium oxide polyhedron obtained by the invention is adjustable.
(5) The {136} plane has a smaller concentration of titanium atoms than all reported crystal planes to which the titanium oxide crystal is exposed, resulting in excellent photodegradation performance and electrochemical performance.
Drawings
Fig. 1 shows electron microscope scans of the products obtained in example 1 and example 2, wherein (a) and (c) show electron microscope scans of the microparticles corresponding to example 1 at 15000 times and 3000 times, respectively, and (b) and (d) show electron microscope scans of the microparticles corresponding to example 2 at 15000 times and 3000 times, respectively. As can be seen from fig. 1, the polyhedron mainly exposing the {101} and {001} faces gradually becomes a polyhedron mainly exposing the {136} faces by etching.
FIG. 2 is a scanning electron microscope image of the product obtained in example 6, wherein (a) corresponds to 100000 times and (b) corresponds to 50000 times, and the product is a polyhedral nanoparticle mainly exposing {101} and {001 }.
FIG. 3 is a graph showing photodegradation performance curves corresponding to the titanium oxide crystals in example 1 and example 2.
FIG. 4 is a graph showing the It curves corresponding to the titanium oxide crystals in example 1 and example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
Example 1: synthesis of a titanium oxide polyhedron, 0.15g of titanyl sulfate and 0.6ml of HF (40 wt%) were dissolved in 120ml of distilled water, after treatment in an ultrasonic apparatus for 20 minutes, the solution was transferred to a reactor, reacted at 160℃for 8 hours, cooled to room temperature, the supernatant was poured out, washed 3 times with absolute ethanol, and then dried in an oven at 80℃for 24 hours, and a solid sample was collected. As shown in FIG. 1 (a), the synthesized crystals were titanium oxide polyhedral particles having a size of about 2 to 3 μm and exposed to {101} and {001} crystal planes, and the dried samples were calcined in air for 4 hours at 800 ℃.
Example 2: {136} planes are carved on the titanium oxide polyhedron: 10ml of 0.3mol/LHF was used as etching solution, which was then transferred to a polytetrafluoroethylene liner with 0.2g TiO 2 Immersing in etching liquid, ultrasonic treating, stirring, and sealing with stainless steel autoclave. The hydrothermal etching treatment was performed at 170 ℃ for 6 hours. After the autoclave was cooled, the reaction solution was taken out of the reactor and washed with ethanol or deionized water. The samples were centrifuged in a centrifuge tube and then dried in air at 80℃for 12h.
Example 3: similar to the procedure of example 2, but in the etching, etching was controlledThe {136} plane ratio is controlled. The etching time is 3h, and TiO with different crystal face ratios consisting of {136}, {101} and {001} faces can be obtained 2 。
Example 4: the remainder was identical to example 1, except that: in the preparation of anatase titanium oxide crystals, the titanium salt was replaced with titanium fluoride, the amount was changed to 0.12g, and the other conditions were unchanged, and the obtained crystals were also polyhedrons having exposed {001} and {101} crystal planes and having a size of about 2 to 3. Mu.m.
Example 5: the remainder was identical to example 1, except that: in the preparation of anatase titanium oxide crystals, the titanium salt was replaced with titanium sulfate, the amount was changed to 0.25g, and the other conditions were unchanged, and the obtained crystals were also polyhedrons having exposed {001} and {101} crystal planes and having a size of about 2 to 3. Mu.m.
Example 6: the remainder was identical to example 1, except that: in preparing anatase titanium oxide crystals, the titanium source was replaced with tetrabutyl titanate in an amount of 5ml, and 6ml of H was added 2 O 2 (30%) HF was added to 0.8ml, and the resulting crystal was also a polyhedron exposing {001} and {101} crystal planes, but having a size of about 50 to 200nm, as shown in FIG. 2 (a, b).
Example 7: the remainder was identical to example 2, except that: by using the polyhedron of example 6 as a precursor for etching, polyhedrons exposing different proportions of {136} faces with dimensions of about 50 to 200nm can be obtained by controlling the etching time.
Example 8: the remainder was identical to example 2, except that: sulfuric acid is used for replacing hydrofluoric acid, the sulfuric acid concentration is 0.2mol/L, the etching temperature is 170 ℃, the etching rate is one time of that of the hydrofluoric acid, and the etching is carried out for 3 hours to obtain the particles with the same etching degree as that of FIG. 1 b.
Example 9: the remainder was identical to example 2, except that: nitric acid is used for replacing hydrofluoric acid, the nitric acid concentration is 0.3mol/L, the etching temperature is 170 ℃, the etching rate is slower than that of the hydrofluoric acid, and the etching is carried out for 12 hours to obtain particles with the same etching degree as that of FIG. 1 b.
Example 10: the remainder was identical to example 2, except that: oxalic acid is used for replacing hydrofluoric acid, the oxalic acid concentration is 0.3mol/L, the etching temperature is 170 ℃, the etching rate is slower than that of the hydrofluoric acid, and the etching is carried out for 24 hours to obtain particles with the same etching degree as that of FIG. 1 b.
Example 11: photodegradation performance test of titanium oxide polyhedron: 100ml of rhodamine b solution with the concentration of 5mg/L and 10mg of the catalyst are respectively added into a 250ml photodegradable quartz glass dish by taking the titanium oxide polyhedral product obtained in the embodiment as a catalyst, the heights of the quartz glass dish and a light source are kept consistent each time, circulating water is opened, and the constant temperature treatment of an experiment is carried out. The stirrer was turned on and stirred under dark conditions for 30min until the degradation solution and the catalyst reached adsorption equilibrium. After the reaction reached adsorption equilibrium, a xenon light lamp was turned on and the degradation liquid was irradiated, 4ml of the degradation liquid was taken out at intervals and immediately centrifuged, and then the supernatant was analyzed using a Hitachi U-3010 uv-vis spectrometer. The experimental results show that the degradation rate of the {136} crystal face-engraved sample obtained in example 2 is that of the TiO obtained in example 1 2 1.39 times as large as the mother crystal as shown in FIG. 3.
Example 12: photodegradation performance test of titanium oxide polyhedron: taking the titanium oxide polyhedral product obtained in the embodiment as a catalyst, putting 5mg of the catalyst and 0.5mg of carbon black into a solution with the molar ratio of ethylene glycol to N, N-dimethylformamide of 3:1, carrying out ultrasonic treatment for 60min, and uniformly coating the solution on the conductive surface of the FTO conductive glass. It was used as a working electrode for It testing in an electrochemical workstation. Experimental results show that the photocurrent intensity of the {136} crystal face-engraved sample obtained in example 2 is that of the TiO obtained in example 1 2 1.88 times as large as the mother crystal as shown in fig. 4.
Claims (3)
1. The preparation method of the anatase titanium oxide polyhedral nano/micron photocatalyst with exposed high-index {136} surface is characterized by comprising the following steps:
(1) Synthesizing polyhedral mother crystals: dissolving a titanium source and an acid in distilled water according to the molar ratio of 0.02-300, treating the mixture in an ultrasonic instrument for 10-20 min, transferring the solution into a reactor, reacting for 2-48 h at 50-400 ℃, cooling to room temperature, pouring out supernatant, washing for 3-5 times by using absolute ethyl alcohol, drying for 8-24 h in an oven to obtain solid, namely titanium oxide polyhedral particles exposing {101} and {001} crystal faces, and calcining the dried sample at 300-1000 ℃ for 1-48 h to obtain titanium oxide polyhedral mother crystals; the titanium source is one of tetrabutyl titanate, titanium sulfate, titanyl sulfate or titanium fluoride;
(2) Etching to obtain a high-index surface: placing the titanium oxide polyhedral mother crystal obtained in the step (1) in acid with the pH value of 0.1-0.9, wherein the acid is one of hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, citric acid and ascorbic acid, carrying out ultrasonic treatment for 10-20 min, transferring the solution into a reactor, etching at 170-250 ℃ for 3-24 h, cooling to room temperature, washing with absolute ethyl alcohol for 3-5 times, centrifuging to collect solid, and drying in an oven for 8-24 h to obtain the solid, namely the titanium oxide polyhedral particles with exposed {136} crystal faces.
2. The method for preparing an anatase titania polyhedral nano/micro photocatalyst exposing high-index {136} faces according to claim 1, wherein the acid in the step (1) is one of hydrochloric acid, sulfuric acid, hydrofluoric acid, oxalic acid, citric acid, and ascorbic acid.
3. The method for preparing an anatase titania polyhedral nano/micro photocatalyst with exposed high-index {136} faces according to claim 1, wherein the drying temperature is 60-80 ℃ in the step (1) and the step (2).
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