CN112028119B - Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal - Google Patents

Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal Download PDF

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CN112028119B
CN112028119B CN202010943643.5A CN202010943643A CN112028119B CN 112028119 B CN112028119 B CN 112028119B CN 202010943643 A CN202010943643 A CN 202010943643A CN 112028119 B CN112028119 B CN 112028119B
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杜意恩
牛宪军
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Jinzhong University
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Abstract

The invention discloses anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 A preparation method and application of the nanocrystalline. The method takes tetraisopropyl titanate as a titanium source, absolute ethyl alcohol as a solvent, hydrofluoric acid or hydrofluoric acid and hydrogen peroxide as a morphology control agent, and synthesizes {101}, {100} and {111} -crystal face co-exposed square anatase type TiO by a sol-gel method 2 And (4) nanocrystals. The invention prepares the square anatase TiO 2 The photocatalyst can be applied to photocatalytic degradation of organic pollutants such as rhodamine B, methylene blue, p-nitrophenol and the like, and can also be applied to solar cells and cosmetics. The preparation method adopted by the invention has the advantages of simple flow, short production period, strong controllability and low synthesis cost, meets the requirement of green chemistry and is suitable for industrial production.

Description

Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal
Technical Field
The invention belongs to the technical field of nanocrystalline materials, and particularly relates to {101}, {100} and {111} -anatase type TiO with exposed crystal faces 2 A preparation method and application of the nanocrystal.
Background
In 1972, nippon scientists Fujishima and Honda discovered TiO in the study 2 The electrode can photolyze water to prepare H 2 This report has attracted the attention of scientists worldwide. In view of TiO 2 The photocatalyst has the advantages of biological and chemical inertness, strong photooxidation capability, long-term stability to light and chemical corrosion, no toxicity, no pollution, low price and the like, so that the photocatalyst has potential application prospects in the aspects of photocatalysis, air purification, lithium ion batteries, solar batteries, water purification and the like, and is expected to solve the problems of world energy and environmental crisis. TiO 2 2 There are three major crystalline forms in nature: anatase type,Rutile and brookite. Among the three forms, anatase type TiO 2 Have been widely studied because of exhibiting the highest photocatalytic performance in photocatalytic degradation of organic pollutants and solar cells. Since the photocatalytic reaction occurs on the surface of the catalyst, controlling the surface structure of the catalyst is crucial to improving the catalytic activity of the catalyst.
Since Wen reported the preparation of {010} crystal plane exposed anatase TiO by using layered titanic acid 2 Designing and synthesizing TiO with specific morphology and high-activity crystal face exposure from nanocrystal 2 Has received extensive attention from researchers. Anatase TiO currently under investigation 2 The high-activity crystal planes mainly comprise {001}, {100} or {010} and {111} crystal planes. The order of increasing surface energy of each crystal face is {101} crystal face (0.44J/m) 2 )<100 or 010 (0.53J/m) 2 )<{001}(0.90J/m 2 ) <{111} -crystal plane (1.61J/m) 2 ). However, most TiO synthesized due to the rapid decrease of crystal planes having surface energy during crystal growth in general 2 The exposed crystal faces of the crystal are mostly {101} crystal faces, and the practical application of the crystal in photocatalysis and solar cells is severely limited. Therefore, anatase TiO with specific morphology and exposed high-activity crystal face is designed and synthesized 2 It remains a challenge.
In recent years, there have been reports of the preparation of anatase TiO with preferential exposure to {010} or {111} -crystal planes 2 For example, anatase TiO with different morphologies exposing {010} or {111} -crystal face is prepared by taking layered titanate as a precursor through proton exchange, intercalation reaction and stripping reaction 2 However, the preparation process needs a long time, the concentrated hydrochloric acid used in the preparation process belongs to dangerous chemicals and has a large dosage, and the stripping reagent, namely tetramethyl ammonium hydroxide, is expensive and is difficult to produce on a large scale; with TiF 4 Is a titanium source, ammonia water is a morphology control agent, and the square plate-shaped anatase TiO with the {111} crystal face exposed is prepared 2 Microcrystals, but TiF used in the preparation of the microcrystals 4 The hydrolysis rate is very fast, difficult to control during the experiment and expensive. The above reasons lead to the resultThe product has higher price and is difficult to realize industrial large-scale production. Thus, the green synthesis has a greater proportion of {101}, {100}, and {111} -crystal plane co-exposed anatase TiO 2 Nanocrystals are very important.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide anatase TiO with co-exposed {101}, {100} and {111} crystal planes 2 A preparation method and application of the nanocrystalline.
To achieve the objects of the present invention, the inventors have combined themselves with many years of anatase TiO modification 2 The research experience of the nanocrystalline material creatively provides that anhydrous ethanol and tetraisopropyl titanate are used as starting materials, and a sol-gel method is utilized to prepare the co-exposed {101}, {100} and {111} crystal face anatase type TiO 2 The anhydrous ethanol and the tetraisopropyl titanate used by the method have rich sources and low price, and the prepared {101}, {100} and {111} -crystal faces are exposed to the anatase TiO 2 The nano-crystalline has controllable particle size and morphology, strong controllability, short production period, green and environment-friendly production process, low energy consumption and easy industrial implementation.
Specifically, the technical scheme of the invention comprises the following steps: anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 The preparation method of the nanocrystalline comprises the steps of taking tetraisopropyl titanate as a titanium source, taking absolute ethyl alcohol as a solvent, adding a morphology control agent, and synthesizing square anatase TiO with co-exposed crystal faces of {101}, {100} and {111} -by a sol-gel method 2 And (4) nanocrystal. The morphology control agent is hydrofluoric acid or a mixed solution of hydrofluoric acid and hydrogen peroxide, and in the mixed solution, the molar ratio of hydrogen fluoride in the hydrofluoric acid to hydrogen peroxide in the hydrogen peroxide is 1: (0.4-3).
Further preferably, the {101}, {100}, and {111} -crystal faces co-exposed anatase TiO form as described above 2 The preparation method of the nanocrystalline specifically comprises the following steps:
a. preparing a titanic acid sol: according to the volume ratio of absolute ethyl alcohol to tetraisopropyl titanate of (2.5-10): 1, putting absolute ethyl alcohol into a reaction container, putting the reaction container into a water bath containing an ice-water mixture, dropwise adding tetraisopropyl titanate under the stirring condition, and uniformly mixing to obtain transparent titanic acid sol;
b. preparation of titanium dioxide gel: adding the titanic acid sol prepared in the step a into a hydrothermal reaction kettle, dropwise adding a morphology control agent under the stirring condition, uniformly mixing, carrying out solvothermal reaction for 6-48 h at the reaction temperature of 120-180 ℃, cooling to room temperature, taking out, carrying out suction filtration on the obtained product, and cleaning with distilled water until the filtrate is neutral; then drying the obtained product at 80-100 ℃ to prepare titanium dioxide gel;
c {101}, {100} and {111} -crystal face co-exposed anatase TiO 2 And (3) synthesis of nanocrystals: b, grinding the titanium dioxide gel prepared in the step b, putting the ground titanium dioxide gel into a muffle furnace, heating the ground titanium dioxide gel for 1 to 6 hours at the temperature of between 300 and 500 ℃, and preparing the anatase TiO with the square blocks mainly exposed by the {101}, {100} and {111} -crystal faces at the heating rate of between 2 and 10 ℃/min 2 And (4) nanocrystals.
Further preferably, {101}, {100}, and {111} -crystal plane co-exposed anatase TiO as described above 2 In the preparation method of the nanocrystalline, when the morphology control agent is hydrofluoric acid, the molar ratio of hydrogen fluoride in the hydrofluoric acid to tetraisopropyl titanate in the step a is 1: (3.6-5.0).
Further preferably, the {101}, {100}, and {111} -crystal faces co-exposed anatase TiO form as described above 2 According to the preparation method of the nanocrystalline, when the morphology control agent is a mixed solution of hydrofluoric acid and hydrogen peroxide, the molar ratio of hydrogen fluoride in the hydrofluoric acid to hydrogen peroxide in the hydrogen peroxide is 1: (1.0-2.2), wherein the molar ratio of hydrogen fluoride in hydrofluoric acid to tetraisopropyl titanate in the step a is 1: (4.4-8.7).
Further preferably, {101}, {100}, and {111} -crystal plane co-exposed anatase TiO as described above 2 And c, preparing the nanocrystal, wherein the reaction time in the step b is 12-24 hours, and the reaction temperature is 160-180 ℃.
In addition, the invention also provides {101}, {100} and {111} -crystal face-co-exposed anatase type TiO prepared by the preparation method 2 And (4) nanocrystal. The {101}, {100} and {111} crystal planes prepared by the invention are exposed togetherBare diamond-like anatase TiO 2 The nanocrystalline can be applied to photocatalytic degradation of organic pollutants such as rhodamine B, methylene blue, p-nitrophenol and the like, can also be applied to cosmetics, and can also be applied to solar cells.
Compared with the prior art, the preparation method of the invention has the following advantages and remarkable progress:
(1) The raw materials of absolute ethyl alcohol and tetraisopropyl titanate used in the invention are cheap and easy to obtain;
(2) The method adopted by the invention is a sol-gel method and a solid phase sintering method, and has the advantages of simple flow, short production period, strong controllability and low synthesis cost;
(3) The method has no pollution, simple preparation process and good repeatability, meets the requirement of green chemistry and is suitable for industrial production;
(4) The {101}, {100} and {111} crystal faces prepared by the invention are co-exposed anatase TiO 2 The nano-crystalline has high purity and uniform particle size distribution, and can effectively improve the degradation performance of organic dye, the ultraviolet resistance of sunscreen cream and the photovoltaic performance of solar cells.
Drawings
FIG. 1 is a graph showing anatase type TiO obtained in example 1 by solvothermally treating a tetraisopropyl titanate ethanol solution having a content of 0.5 to 2.0mLHF at 180 ℃ 2 XRD diffraction patterns of (a) 0.5HF-T180, (b) 1.0HF-T180, (c) 1.5HF-T180, and (d) 2.0 HF-T180;
FIG. 2 is a graph showing anatase type TiO obtained in example 2 by solvothermally treating a tetraisopropyl titanate ethanol solution having a content of 1.5 and 2.0mLHF at 120 deg.C 2 (a) 1.5HF-T120, and (b) an XRD diffraction pattern of 2.0 HF-T120;
FIG. 3 shows that the content of heat-treated solvent in example 3 at 180 ℃ is 0.5-2.0 mLHF and 5mL H 2 O 2 Anatase type TiO obtained from tetraisopropyl titanate ethanol solution 2 (a)0.5HF-5H 2 O 2 -T180、(b)1.0HF-5H 2 O 2 -T180、(c) 1.5HF-5H 2 O 2 -T180 and (d) 2.0HF-5H 2 O 2 -XRD diffraction pattern of T180;
FIG. 4 shows the temperature of 130 ℃ in example 4The heat treatment content of the solvent is 1.0-2.0 mLHF and 5mLH 2 O 2 Anatase type TiO obtained from tetraisopropyl titanate ethanol solution 2 (a)1.0HF-5H 2 O 2 -T130、(b)1.5HF-5H 2 O 2 -T130 and (c) 2.0HF-5H 2 O 2 -XRD diffraction pattern of T180;
FIG. 5 is a scanning electron micrograph of the synthesized products of example 1 (a) 0.5HF-T180, (b) 1.0HF-T180, (c) 1.5HF-T180 and (d) 2.0HF-T180 at a solvothermal treatment temperature of 180 ℃ and an HF content of 0.5 to 2.0 mL;
FIG. 6 shows the results of example 3, in which the temperature of the solvothermal treatment was 180 ℃, the HF content was 0.5 to 2.0mL, and H was added 2 O 2 At 5mL, the synthesized product (a) was 0.5HF-5H 2 O 2 -T180、(b)1.0HF-5H 2 O 2 -T180、(c)1.5HF-5H 2 O 2 -T180 and (d) 2.0HF-5H 2 O 2 -scanning electron microscopy images of T180;
FIG. 7 is a transmission electron micrograph of the synthesized products (a-c) 1.0HF-T180, (d-f) 1.5HF-T180 and (g-i) 2.0HF-T180 in example 1 at a solvothermal treatment temperature of 180 ℃ and an HF content of 1.0 to 2.0 mL;
FIG. 8 shows the results of example 3, wherein the solution heat treatment temperature is 180 ℃, the HF content is 1.0-2.0 mL, and H 2 O 2 At 5mL, the synthesized product (a-c) is 1.0HF-5H 2 O 2 -T180、(d-f)1.5HF-5H 2 O 2 -T180 and (g-i) 2.0HF-5H 2 O 2 -transmission electron microscopy at T180;
FIG. 9 shows the degradation rate of rhodamine B solution as a function of illumination time in the presence and absence of catalyst in example 1;
FIG. 10 shows the degradation rate of rhodamine B solution as a function of time in the presence and absence of catalyst in example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. In addition, the specific technical operation steps or conditions not indicated in the examples are all performed according to the technical or conditions described in the literature in the field or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
(1) Preparing a titanic acid sol: measuring 200mL of absolute ethyl alcohol into a round-bottom flask by using a measuring cylinder, placing the round-bottom flask into a water bath containing an ice-water mixture, dropwise adding 50mL of tetraisopropyl titanate (0.166 mol) under the stirring condition, and mixing uniformly to obtain transparent titanic acid sol;
(2) Preparing titanium dioxide gel: respectively transferring 60mL of the titanic acid sol prepared in the step (1) into a hydrothermal reaction kettle, dropwise adding 0.5-2.0 mL of HF solution (0.011-0.045 mol) under the stirring condition, mixing uniformly, placing in a constant-temperature air-blowing drying box with the set temperature of 180 ℃, carrying out solvent thermal reaction for 24 hours, cooling to room temperature, taking out, carrying out suction filtration on the obtained product by adopting a circulating water type multi-purpose vacuum pump, and cleaning by using a large amount of distilled water until the filtrate is neutral; then the obtained product is placed in a constant temperature air blast drying oven to be dried at 100 ℃ to prepare titanium dioxide gel;
(3) Synthesis of {101}, {100}, and {111} -crystal plane co-exposed anatase TiO 2 And (3) nanocrystal: grinding the titanium dioxide gel sample prepared in the step (2) in a mortar, transferring the ground titanium dioxide gel sample into a corundum crucible, heating the corundum crucible in a muffle furnace at 450 ℃ for 3h at the heating rate of 5 ℃/min, and preparing square anatase TiO (anatase type TiO) with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystalline, labelled xHF-TiO 2 And x is the volume of HF, and the shape of the HF is mainly square.
As can be seen from FIG. 1 (a), the diffraction peaks at 2 θ values of 25.48 °, 38.20 ° and 48.10 ° correspond to anatase type TiO, respectively 2 The (101), (004) and (200) crystal planes of the crystal are consistent with the characteristic diffraction peaks of anatase standard card PDF # 21-1272; in addition, the most intense diffraction peak at the 2 theta value of 11.94 degrees corresponds to the interplanar spacing of 0.741nm, and belongs to the typical diffraction peak of the lamellar compound. Thus, when HF was 0.5mL (0.011 mol), the synthesized samples were a layered compound and anatase TiO 2 A mixture of (a). As can be seen from 1 (b), the value of 2 θ isDiffraction peaks at 25.38 °, 38.03 °, 48.09 °, 54.05 °, 54.88 ° and 62.82 correspond to anatase TiO, respectively 2 The (101), (004), (200), (105) and (204) crystal planes of the crystal planes are consistent with the characteristic diffraction peaks of anatase standard card PDF # 21-1272; in addition, the diffraction peak with the 2 theta value of 11.42 degrees is also provided, the corresponding interplanar spacing is 0.774nm, and the diffraction peak belongs to the typical diffraction peak of a layered compound. Thus, when HF was 1.0mL, the synthesized sample was predominantly anatase TiO 2 But also small amounts of lamellar compounds. As can be seen from FIGS. 1 (c) and (d), when HF is 1.5mL (0.034 mol) and 2.0mL (0.045 mol), diffraction peaks at 2 θ values of 25.34 °, 36.97 °, 37.88 °, 38.70 °, 48.04 °, 54.08 °, 55.16 °, 62.76 °, 68.92 °, 70.40 ° and 75.08 ° correspond to anatase TiO, respectively 2 The (101), (103), (004), (112), (200), (105), (211), (204), (116), (220) and (215) crystal planes of (A) coincide with the characteristic diffraction peaks of anatase standard card PDF #21-1272, and the intensity of the diffraction peaks decreases when HF is increased from 1.5mL (0.034 mol) to 2.0mL (0.045 mol), indicating that the crystal size decreases and the crystallinity decreases, which may be caused by the increased HF content, corrosiveness to the generated crystals, and decreased crystallinity of the particles. The particle size of the crystal can be estimated by Scherrer equation (d =0.89 λ/β cos θ), where λ is the wavelength of X-ray and β is the half-width of the diffraction peak. 1.5HF-TiO calculated according to the Sheer equation 2 And 2.0HF-TiO 2 The particle sizes of (a) and (b) were 19.5nm and 18.4nm, respectively.
As is clear from the above, in example 1, anatase type TiO was synthesized at 1.5mL (0.034 mol) and 2.0mL (0.045 mol) of HF 2 And (4) nanocrystals.
FIG. 5 is the anatase TiO synthesized in example 1 2 The synthesized nanocrystalline particles are mostly cubic, and have good crystallinity and narrow particle size distribution of about 20 to 40nm as can be seen from the scanning electron microscope image of (A).
FIG. 7 shows anatase type TiO synthesized in example 1 2 Transmission electron micrograph of (D), from which it can be seen that TiO was synthesized 2 The appearance of the nanocrystalline is mostly cubic. In FIG. 7, the interplanar spacing is 0.189nm (0.190 n)m), 0.235nm (0.236 nm or 0.240 nm), 0.352nm (0.354 nm) and 0.472nm, corresponding to anatase TiO respectively 2 (200), (004), (101)/(011) and (002) crystal planes of (1), (2), (011) and (004), wherein the angle between the (101) and (004) crystal planes is 68.3 DEG, and TiO according to anatase type 2 The results of theoretical calculation of the (101) and (004) crystal planes are consistent, which indicates that the exposed crystal plane is a {010} crystal plane; (101) And (011) crystal plane at 82 DEG, and TiO according to anatase type 2 The results of theoretical calculations for the (101) and (011) crystal planes of (A) are consistent, indicating that the exposed crystal plane is perpendicular to the {111} crystal plane. (200) The angle between the (004) and the (004) crystal face is 90 DEG, and the angle is equal to that of the anatase type TiO 2 The results of theoretical calculation of the (200) and (004) crystal planes are consistent, which indicates that the exposed crystal plane is a {010} crystal plane; further, the stripe of the crystal planes of (200) and (101) parallel to one side of the square crystal indicates that the side-exposed crystal planes are {100} and {101} crystal planes.
As can be seen from the above, example 1 synthesized an anatase type TiO having co-exposed {101}, {100}, and {111} -crystal planes 2 And (4) nanocrystals.
(4) TiO prepared in this example 2 Application of nanocrystalline in photocatalytic degradation of organic pollutant rhodamine B
TiO prepared in this example 2 The nanocrystalline can be used for photodegradation of organic wastewater, such as wastewater containing methylene blue, rhodamine B, methyl orange or p-nitrophenol, and 1.0g of the nanocrystalline can treat 1.0-5.0 kg of organic wastewater containing 2.5-15 ppm of methylene blue, rhodamine B or phenol. 75mg of the anatase TiO co-exposed on the {010}, {101}, {100} and {111} -crystal planes obtained in example 1 were weighed out 2 Adding the nanocrystalline sample into a 200mL beaker containing 150mL7.5ppm rhodamine B solution, stirring for 30min, and then placing in the dark for 24h to ensure that the rhodamine B is in TiO 2 The adsorption/desorption equilibrium of the nanocrystal surface is achieved. Before irradiation, the suspension was stirred vigorously in the dark for 30min, and then irradiated under stirring under a 175W high-pressure mercury lamp, the distance of the lamp from the methylene blue solution being 40cm. Every 15min, 4mL of the suspension was placed in a 10mL centrifuge tube and centrifuged to remove TiO 2 And (4) nanocrystals. Degradation Rate of rhodamine B ultraviolet radiation was measured by using a TU-1901 type ultraviolet spectrophotometerAnd determining the concentration change of the previous and next rhodamine B solutions. The test results are shown in fig. 9, respectively.
As can be seen from FIG. 9, the sequence of the degradation efficiency of rhodamine B is blank (1.71%) when the ultraviolet light is irradiated for 120min<0.5HF-T180(5.18％)<1.0HF-T180(5.38％)<2.0HF-T180(42.26％)<Bodi- TiO 2 (43.95％)<1.5HF-T180 (74.72%). That is, at 120min, 1.5HF-T180 anatase type TiO co-exposed with {010}, {101}, {100}, and {111} -crystal planes 2 When the nanocrystalline is used as a catalyst, the degradation rate of rhodamine B is 74.72%. When the illumination time is continuously prolonged to 210min and 1.5HF-T180 is used as a catalyst, the degradation rate of the rhodamine B is as high as 92.83 percent.
As can be seen from the above, the {101}, {100}, and {111} -crystal planes synthesized in example 1 co-exposed TiO 2 The nanocrystalline has application value in photocatalytic degradation of organic pollutants (such as rhodamine B).
Example 2:
(1) Preparing a titanic acid sol: measuring 100mL of absolute ethyl alcohol in a round-bottom flask by using a measuring cylinder, placing the round-bottom flask in a water bath containing an ice-water mixture, dropwise adding 25mL of tetraisopropyl titanate under the stirring condition, and uniformly mixing to obtain transparent titanic acid sol;
(2) Preparing titanium dioxide gel: respectively transferring 60mL of the titanic acid sol prepared in the step (1) into a hydrothermal reaction kettle, dropwise adding 1.5mL (0.034 mol) and 2.0mL (0.045 mol) of HF solutions under the stirring condition, mixing uniformly, placing in a constant-temperature air-blast drying oven with a set temperature of 120 ℃, carrying out solvothermal reaction for 6h, cooling to room temperature, taking out, carrying out suction filtration on the obtained product by adopting a circulating water type multi-purpose vacuum pump, and washing by using a large amount of distilled water until the filtrate is neutral; then the obtained product is placed in a constant temperature air blast drying oven to be dried at 100 ℃ to prepare titanium dioxide gel;
(3) Synthesis of {010}, {101}, {100} and {111} -crystal face co-exposed anatase TiO 2 Nano-crystalline: grinding the titanium dioxide gel sample prepared in the step (2) in a mortar, transferring the ground titanium dioxide gel sample into a corundum crucible, heating the corundum crucible in a muffle furnace at 300 ℃ for 6 hours at the heating rate of 2 ℃/min, and preparing {010}, {101}, {100} and {010}, wherein{111} -crystal face-co-exposed anatase TiO cube 2 Nanocrystalline, labelled xHF-TiO 2 And x is the volume of HF, and the morphology of the HF is mainly square.
As can be seen from FIGS. 2 (a) and (b), when HF is 1.5mL (0.034 mol) and 2.0mL (0.045 mol), diffraction peaks at 2 θ values of 25.30 °, 36.98 °, 37.86 °, 38.60 °, 48.08 °, 54.04 °, 55.10 °, 62.80 °, 70.34 ° and 75.26 ° correspond to anatase TiO, respectively 2 The (101), (103), (004), (112), (200), (105), (211), (204), (220) and (215) crystal planes of (A) coincide with the characteristic diffraction peaks of anatase standard card PDF # 21-1272.
As can be seen from the above, anatase type TiO was synthesized in example 2 2 And (4) nanocrystals.
Example 3:
(1) Preparing titanic acid sol: measuring 210mL of absolute ethyl alcohol into a round-bottom flask by using a measuring cylinder, placing the round-bottom flask into a water bath containing an ice-water mixture, dropwise adding 60mL of tetraisopropyl titanate (0.199 mol) under the stirring condition, and mixing uniformly to obtain transparent titanic acid sol;
(2) Preparing titanium dioxide gel: respectively transferring 60mL of the titanic acid sol prepared in the step (1) into a hydrothermal reaction kettle, dropwise adding 0.5-2.0 mL of HF solution (0.011-0.045 mol) under the stirring condition, mixing uniformly, and slowly dropwise adding 5.0mL of H 2 O 2 Uniformly stirring the solution (0.049 mol), placing the solution in a constant-temperature air-blast drying box with the set temperature of 180 ℃, carrying out solvothermal reaction for 24 hours, cooling the solution to room temperature, taking out the solution, carrying out suction filtration on the obtained product by using a circulating water type multipurpose vacuum pump, and cleaning the product by using a large amount of distilled water until the filtrate is neutral; then the obtained product is placed in a constant temperature air blast drying oven to be dried at 100 ℃ to prepare titanium dioxide gel;
(3) Synthesis of {010}, {101}, {100}, and {111} -crystal plane co-exposed anatase TiO 2 And (3) nanocrystal: grinding the titanium dioxide gel sample prepared in the step (2) in a mortar, transferring the ground titanium dioxide gel sample into a corundum crucible, heating the corundum crucible in a muffle furnace at 350 ℃ for 3 hours at the heating rate of 10 ℃/min to prepare the square anatase type with co-exposed crystal faces of {010}, {101}, {100} and {111} -crystal faceTiO 2 Nanocrystals, labeled xHF-5H 2 O 2 -TiO 2 X and 5 are HF and H, respectively 2 O 2 The volume of the solution, its morphology is mainly cubic.
As can be seen from FIG. 3 (a), the diffraction peaks at 2 θ values of 25.30 °, 37.80 °, 48.12 °, 55.10 °, 62.65 °, 70.42 ° and 75.24 ° correspond to anatase type TiO, respectively 2 The (101), (004), (200), (211), (204), (220) and (215) crystal planes of (a) coincide with the characteristic diffraction peaks of anatase standard card PDF #21-1272, and in addition, there are two diffraction peaks at 2 θ values of 30.14 ° and 34.61 °, which belong to impurity diffraction peaks. Thus, when HF is 0.5mL (0.011 mol), the synthesized sample is predominantly anatase TiO 2 . As can be seen from FIGS. 3 (b-d), when HF is 1.0 to 2.0mL (0.023 to 0.045 mol), the diffraction peaks at 2 θ values of 25.26 °, 37.12 °, 37.90 °, 38.62 °, 48.04 °, 53.96 °, 55.04 °, 62.84 °, 68.96 °, 70.57 ° and 75.06 ° correspond to anatase TiO, respectively 2 The (101), (103), (004), (112), (200), (105), (211), (204), (116), (220) and (215) crystal planes of (a) coincide with the characteristic diffraction peaks of anatase standard card PDF #21-1272, and the diffraction peak intensity increases as HF increases from 1.0mL to 2.0mL, indicating that the crystal size increases and the crystallinity increases. The particle size of the crystal can be estimated by Scherrer equation (d =0.89 λ/β cos θ), where λ is the wavelength of X-ray and β is the half-width of the diffraction peak. 1.5HF-TiO calculated according to the Sheer equation 2 And 2.0HF-TiO 2 The particle sizes of (a) are 16.3nm, 19.3 nm and 19.8nm, respectively.
As is clear from the above, in example 3, HF was 1.0mL (0.023 mol), 1.5mL (0.034 mol), 2.0mL (0.045 mol) and H 2 O 2 At 5mL (0.049 mol), anatase type TiO was synthesized 2 And (4) nanocrystal.
FIG. 6 is the anatase TiO synthesized in example 3 2 The scanning electron microscopic image of (2) shows that the synthesized nanocrystalline particles are mostly cubic, have good crystallinity and narrow particle size distribution of about 10 to 30nm.
FIG. 8 is the anatase TiO synthesized in example 3 2 Transmission electron micrograph of (D), from which it can be seen that TiO was synthesized 2 The appearance of the nanocrystalline is mostly cubic. In FIG. 8, interplanar spacings of 0.189nm (0.190 nm) and 0.352nm (0.354 nm) and 0.472nm correspond to anatase TiO, respectively 2 Of (200) and (101)/(011) crystal planes, wherein the angle between the (101) and (011) crystal planes is 82 DEG, compared to TiO according to anatase type 2 The theoretical calculation results of the (101) and (011) crystal planes are consistent, which indicates that the exposed crystal plane is vertical to the {111} crystal plane; further, the stripe of the crystal planes of (200) and (101) parallel one side of the square crystal, indicating that the side-exposed crystal planes are {100} and {101} crystal planes.
As can be seen from the above, example 3 synthesized anatase TiO having co-exposed {101}, {100}, and {111} -crystal planes 2 And (4) nanocrystal.
(4) TiO prepared in this example 2 Application of nanocrystalline in photocatalytic degradation of organic pollutant rhodamine B
TiO prepared in this example 2 The nanocrystalline can be used for photodegradation of organic wastewater, such as wastewater containing methylene blue, rhodamine B, methyl orange or p-nitrophenol, and 1.0g of the nanocrystalline can treat 1.0-5.0 kg of organic wastewater containing 2.5-15 ppm of methylene blue, rhodamine B or phenol. 75mg of the anatase TiO {101}, {100}, and {111} -crystal face co-exposed obtained in example 1 were weighed 2 Adding the nanocrystal sample into a 200mL beaker containing 150mL of 7.5ppm rhodamine B solution, stirring for 30min, and then placing in a dark place for 24h to ensure that the rhodamine B is in TiO 2 The surface of the nano crystal reaches the adsorption/desorption balance. Before irradiation, the suspension was stirred vigorously in the dark for 30min, and then irradiated under stirring under a 175W high-pressure mercury lamp, the distance of the lamp from the methylene blue solution being 40cm. Every 15min, 4mL of the suspension was placed in a 10mL centrifuge tube and centrifuged to remove the TiO 2 And (4) nanocrystals. The degradation rate of rhodamine B is determined by measuring the concentration change of rhodamine B solution before and after the irradiation of ultraviolet light by using a TU-1901 type ultraviolet spectrophotometer. The test results are shown in fig. 10, respectively.
As can be seen from FIG. 10, the sequence of the degradation efficiency of rhodamine B is blank (1.7%) when the ultraviolet light is irradiated for 120min<1.0HF-5H 2 O 2 -T180(3.34％)<Bodi-TiO 2 (43.95％)<2.0HF-5H 2 O 2 -T180(67.5％) <1.5HF-5H 2 O 2 -T180(76.3％)<1.0HF-5H 2 O 2 -T180 (94.5%). That is, at 120min, 1.0HF-5H with {101}, {100}, and {111} -crystal planes co-exposed 2 O 2 -T180 anatase TiO 2 When the nanocrystalline is used as a catalyst, the degradation rate of rhodamine B is 94.5%. Continuously prolonging the illumination time to 210min, and adding 1.0HF-5H 2 O 2 when-T180 is a catalyst, the degradation rate of rhodamine B is as high as 99.9%.
As can be seen from the above, the {101}, {100}, and {111} -crystal planes synthesized in example 3 co-exposed TiO 2 The nanocrystalline has application value in photocatalytic degradation of organic pollutants (such as rhodamine B).
Example 4:
(1) Preparing titanic acid sol: measuring 150mL of absolute ethyl alcohol in a round-bottom flask by using a measuring cylinder, placing the round-bottom flask in a water bath containing an ice-water mixture, dropwise adding 37.5mL of tetraisopropyl titanate under the stirring condition, and mixing uniformly to obtain transparent titanic acid sol;
(2) Preparing titanium dioxide gel: respectively transferring 60mL of the titanic acid sol prepared in the step (1) into a hydrothermal reaction kettle, dropwise adding 1.0-2.0 mL of HF solution (0.023-0.045 mol) under the stirring condition, mixing uniformly, and then slowly dropwise adding 5.0mL of H 2 O 2 Uniformly stirring the solution (0.049 mol), placing the solution in a constant-temperature air-blast drying box with the set temperature of 130 ℃, carrying out solvothermal reaction for 12 hours, cooling the solution to room temperature, taking out the solution, carrying out suction filtration on the obtained product by using a circulating water type multipurpose vacuum pump, and cleaning the product by using a large amount of distilled water until the filtrate is neutral; then placing the obtained product in a constant-temperature air-blast drying oven to dry at 100 ℃ to prepare titanium dioxide gel;
(3) Synthesis of {101}, {100}, and {111} -crystal plane co-exposed anatase TiO 2 Nano-crystalline: grinding the titanium dioxide gel sample prepared in the step (2) in a mortar, transferring the ground titanium dioxide gel sample into a corundum crucible, heating the corundum crucible in a muffle furnace at 350 ℃ for 3 hours at the heating rate of 5 ℃/min, and preparing {010}, {101}, and,{100} and {111} -crystal plane co-exposed cube-like anatase TiO 2 Nanocrystals, labeled xHF-5H 2 O 2 -T130, x and 5 are HF and H, respectively 2 O 2 The volume of the solution, its morphology is mainly cubic.
As can be seen from FIGS. 4 (a-c), when HF is 1.0 to 2.0mL, the diffraction peaks at 2 θ values of 5.32 °, 37.94 °, 48.06 °, 53.94 °, 55.06 °, 62.87 °, 68.76 °, 70.30 ° and 74.84 ° correspond to anatase TiO, respectively 2 The (101), (004), (200), (105), (211), (204), (116), (220) and (215) crystal planes of (A) are consistent with the characteristic diffraction peaks of anatase standard card PDF # 21-1272.
As can be seen from the above, in example 4, {101}, {100}, and {111} -crystal face-co-exposed anatase TiO forms were synthesized 2 And (4) nanocrystals.

Claims (6)

1. Anatase type TiO with co-exposed {101}, {100} and {111} -crystal face 2 The preparation method of the nanocrystalline is characterized in that tetraisopropyl titanate is used as a titanium source, absolute ethyl alcohol is used as a solvent, a morphology control agent is added, and a sol-gel method is utilized to synthesize square anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 A nanocrystal comprising the steps of:
a. preparing a titanic acid sol: according to the volume ratio of absolute ethyl alcohol to tetraisopropyl titanate of (2.5 to 10): 1, putting absolute ethyl alcohol into a reaction container, putting the reaction container into a water bath containing an ice-water mixture, dropwise adding tetraisopropyl titanate under the condition of stirring, and uniformly mixing to obtain transparent titanic acid sol;
b. preparation of titanium dioxide gel: adding the titanic acid sol prepared in the step a into a hydrothermal reaction kettle, dropwise adding a morphology control agent under the stirring condition, uniformly mixing, carrying out solvent thermal reaction for 6 to 48 hours at the reaction temperature of 120 to 180 ℃, cooling to room temperature, taking out, carrying out suction filtration on the obtained product, and cleaning with distilled water until the filtrate is neutral; then drying the obtained product at 80-100 ℃ to prepare titanium dioxide gel;
c. {101}, {100} and {111} -crystal face co-exposed anatase TiO 2 And (3) synthesis of nanocrystals: grinding the titanium dioxide gel prepared in the step b, putting the ground titanium dioxide gel into a muffle furnace, heating the ground titanium dioxide gel for 1 to 6 hours at the temperature of 300 to 500 ℃ at the heating rate of 2 to 10 ℃/min, and preparing the anatase TiO with the square blocks mainly exposed by the {101}, {100} and {111} -crystal faces 2 A nanocrystal;
the morphology control agent is hydrofluoric acid or a mixed solution of hydrofluoric acid and hydrogen peroxide, and in the mixed solution, the molar ratio of hydrogen fluoride in the hydrofluoric acid to hydrogen peroxide in the hydrogen peroxide is 1: (0.4 to 3).
2. The co-exposed anatase TiO crystal planes of {101}, {100}, and {111} -of claim 1 2 The preparation method of the nanocrystalline is characterized in that when the morphology control agent is hydrofluoric acid, the molar ratio of hydrogen fluoride in the hydrofluoric acid to tetraisopropyl titanate in the step a is 1: (3.6 to 5.0).
3. The {101}, {100}, and {111} -crystal plane co-exposed anatase TiO of claim 1 2 The preparation method of the nanocrystalline is characterized in that when the morphology control agent is a mixed solution of hydrofluoric acid and hydrogen peroxide, the molar ratio of hydrogen fluoride in the hydrofluoric acid to hydrogen peroxide in the hydrogen peroxide is 1: (1.0 to 2.2), wherein the molar ratio of hydrogen fluoride in hydrofluoric acid to tetraisopropyl titanate in the step a is 1: (4.4 to 8.7).
4. The co-exposed anatase TiO crystal planes of {101}, {100}, and {111} -of claim 1 2 The preparation method of the nanocrystal is characterized in that the reaction time in the step b is 12 to 24 hours, and the reaction temperature is 160 to 180 ℃.
5. An anatase type TiO having co-exposed {101}, {100}, and {111} -crystal planes obtained by the production method according to any one of claims 1 to 4 2 And (4) nanocrystals.
6. An anatase TiO co-exposed with {101}, {100}, and {111} -crystal planes as defined in claim 5 2 Application of nanocrystalline in photocatalytic degradation of organic pollutants, and application of nanocrystallineThe organic pollutant is one of rhodamine B, methylene blue and p-nitrophenol.
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