CN112387260A - Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof - Google Patents

Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof Download PDF

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CN112387260A
CN112387260A CN202011167648.XA CN202011167648A CN112387260A CN 112387260 A CN112387260 A CN 112387260A CN 202011167648 A CN202011167648 A CN 202011167648A CN 112387260 A CN112387260 A CN 112387260A
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adsorbent
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tio
isopropanol
concentration
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朱利
苏靖婷
肖军
张若虎
崔一平
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Southeast University
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Abstract

The invention discloses a recyclable mesoporous TiO with adjustable surface electrical property2The preparation method of the adsorbent comprises the following steps: (1) mixing isopropanol and deionized water uniformlyThen, adding an acidic solution or an alkaline solution into the solution, and stirring to obtain a solution I; (2) adding an isopropanol solution of diisopropyl di (acetylacetonate) titanate into the solution I, uniformly stirring and centrifuging; (3) washing the precipitate centrifuged in the step (2) with deionized water and isopropanol, drying and grinding to obtain the mesoporous TiO2An adsorbent. The mesoporous TiO prepared by the invention2The adsorbent not only has large specific surface area, but also has abundant active functional groups on the surface, and can adjust the pH of the solution in the preparation process to adjust the mesoporous TiO2The surface of the adsorbent is electrically charged, so that the adsorbent correspondingly shows high-efficiency adsorption capacity to positively or negatively charged pollutants, and the mesoporous TiO2The adsorbent can be regenerated, and the cyclic adsorption is realized.

Description

Recyclable mesoporous TiO with adjustable surface electrical property2Adsorbent and preparation method and application thereof
Technical Field
The invention relates to a recyclable mesoporous TiO with adjustable surface electrical property2A preparation method and application of an adsorbent, belonging to the technical field of functional materials.
Background
In recent years, due to the development of various fields such as medicines, fluorescent materials, organic pesticides, industrial dyes, and the like, a large amount of pollutants such as antibiotics, pesticides, dyes, chemicals, and the like are discharged into the environment through industrial wastewater and domestic sewage, resulting in the pollution of water. In addition, many pollutants contain aromatic hydrocarbon structures, have strong irritation to the skin, are toxic, pathogenic and teratogenic, threaten the health of human beings, and therefore are necessary to treat the pollutants.
Adsorption is a common method for removing contaminants from aqueous environments, but the adsorption process alone can only transfer contaminants from one place to another, and cannot completely remove them. In-situ oxidative degradation of adsorbed contaminants to harmless CO2And H2O, the method is an efficient pollutant treatment strategy. However, conventional adsorbents having high adsorption capacity are generally carbon-based materials, and they are oxidized by a strong oxidant during degradation, resulting in a decrease in adsorption capacity and difficulty in reuse.
Titanium dioxide is used as an environment-friendly, low-cost and high-stability material, and is widely applied to treatment of water pollution. For example, patent CN104874367AMaterial treated chitosan-TiO2Regeneration method of adsorbent2Combined with chitosan for the adsorption of acid dyes, i.e. anionic dyes; in the article of absorption and removal of glyphosate on the surface of high-index {201} titanium dioxide (scientific report on impurity environment, 2018, volume 38, phase 1, page 217-225), high-index crystal face {201} TiO is utilized2Adsorbing and removing the pollutant organophosphorus pesticide glyphosate. However, the surface electrical property of the traditional titanium dioxide adsorbent is not adjustable, so that certain pollutants can be selectively adsorbed only through static electricity, and the traditional titanium dioxide adsorbent has no universality.
Based on the problems, the invention provides the mesoporous TiO with the adjustable surface electrical property, which can be recycled2The preparation method and the application of the adsorbent can adjust the mesoporous TiO by adjusting the pH of the solution in the preparation process2The surface of the adsorbent is electrically charged, so that the adsorbent correspondingly shows high-efficiency adsorption capacity to pollutants with positive charges or negative charges, and after the adsorbed pollutants are degraded by using a strong oxidant, the mesoporous TiO is2The adsorbent can be regenerated, and the cyclic adsorption is realized.
Disclosure of Invention
The invention aims to provide a recyclable mesoporous TiO with adjustable surface electrical property2The preparation method and the application of the adsorbent are used for solving the problems that the adsorbent is easily oxidized and damaged by strong oxidant and TiO2The adsorbent has the problem of adsorption universality to pollutants.
In order to achieve the purpose, the invention adopts the technical scheme that:
recyclable mesoporous TiO with adjustable surface electrical property2The preparation method of the adsorbent comprises the following steps:
(1) uniformly mixing isopropanol and deionized water, adding an acidic solution or an alkaline solution into the mixture, and stirring to obtain a solution I;
(2) adding an isopropanol solution of diisopropyl di (acetylacetonate) titanate into the solution I, uniformly stirring and centrifuging;
(3) washing the precipitate centrifuged in the step (2) with deionized water and isopropanol, drying and grinding to obtain the productTo the mesoporous TiO2An adsorbent.
The volume ratio of the isopropanol, the deionized water and the isopropanol solution of the diisopropyl di (acetylacetonate) titanate is 2:1: 1-4: 1:3, wherein the concentration of the isopropanol solution of the diisopropyl di (acetylacetonate) titanate is 10 mmol/L.
The acid solution is one of hydrochloric acid, acetic acid or sulfuric acid, and the volume ratio of the addition amount of the acid solution to deionized water is 1: 2-1: 10, wherein the concentration of the hydrochloric acid is 37 wt%, the concentration of the acetic acid is 98 wt%, and the concentration of the sulfuric acid is 98 wt%; the alkaline solution is one of ammonia water, sodium hydroxide or potassium hydroxide solution, the volume ratio of the addition amount of the alkaline solution to the deionized water is 1: 2-1: 10, wherein the concentration of the ammonia water is 25-28 wt%, the concentration of the sodium hydroxide solution is 0.1-1 mol/L, and the concentration of the potassium hydroxide is 0.1-1 mol/L.
Recyclable mesoporous TiO prepared by using method and with adjustable surface electrical property2Adsorbent of the TiO2The adsorbent has no lattice structure and belongs to amorphous TiO2(ii) a Has mesoporous structure and large specific surface area, and the surface is rich in active functional groups of hydroxyl and carboxyl.
TiO produced when using acidic solutions in the preparation process2TiO produced by using alkaline solution with positive surface electrical property of adsorbent2The surface electrical property of the adsorbent is negative.
The mesoporous TiO with the recyclable property and the adjustable surface electric property2Use of an adsorbent for adsorbing a positively or negatively charged contaminant. The method comprises the following specific steps: the mesoporous TiO is mixed2The adsorbent is directly mixed with the solution containing the pollutants, and after stirring, solid powder is centrifugally separated.
The initial concentration of the solution containing the pollutants is 1-600 mg/L, and TiO is2The addition amount of the adsorbent is 0.1-10 g/L, the adsorption time is 20 min-3 h, and the adsorption temperature is 25-45 ℃.
After the adsorption process, the separated TiO is centrifuged2Adding strong oxidant into the adsorbent to degrade the adsorbed pollutant to obtain regenerated mesoporous TiO2The adsorbent can be recycled.The strong oxidant is one of potassium persulfate, sodium persulfate, potassium hypochlorite and sodium hypochlorite.
Has the advantages that: the mesoporous TiO which can be recycled and has adjustable surface electrical property provided by the invention2The adsorbent, the preparation method and the application thereof can adjust the mesoporous TiO by adjusting the pH of the solution in the preparation process2The surface of the adsorbent is electrically charged, so that the adsorbent correspondingly shows high-efficiency adsorption capacity to pollutants with positive charges or negative charges, and after the adsorbed pollutants are degraded by using a strong oxidant, the mesoporous TiO is2The adsorbent can be regenerated, and the cyclic adsorption is realized.
Compared with the prior art, the invention has the following advantages:
1. the mesoporous TiO provided by the invention2In the preparation method of the adsorbent, the pH of the preparation environment can be changed by adding an acidic or alkaline solution, so that TiO can be regulated and controlled2The surface electrical property of the adsorbent correspondingly shows high adsorption capacity to pollutants with positive charges or negative charges, and the adsorbent has universality of adsorption application;
2. the mesoporous TiO prepared by the invention2After the adsorbent is adsorbed, the adsorbent can be kept stable through the oxidative degradation process of a strong oxidant, and can be recycled;
3. TiO prepared by the invention2The adsorbent is of a mesoporous structure, has a large specific surface area and a plurality of adsorption sites, is rich in active functional groups on the surface, and has quick and high-capacity adsorption performance on pollutants;
4. the TiO provided by the invention2The adsorbent is synthesized by a simple preparation method at normal temperature and normal pressure, the preparation process is simple and convenient to operate, the cost is low, and the yield is high.
Drawings
FIG. 1 shows TiO prepared in example 12Transmission electron microscopy pictures of the adsorbent;
FIG. 2 shows TiO prepared in example 12Fourier infrared spectra of the adsorbent;
FIG. 3 shows TiO prepared in example 12Absorption spectrum of methylene blue solution in adsorption process of adsorbent and application of methylene blue solution in adsorption processPhoto comparison before and after adsorption.
Detailed Description
The mesoporous TiO with the adjustable surface electrical property can be recycled2The preparation method of the adsorbent comprises the steps of uniformly mixing isopropanol, deionized water and an acidic solution or an alkaline solution, adding an isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) into the mixture, stirring, centrifugally cleaning and drying to obtain the mesoporous TiO2An adsorbent powder. When acid solution is used in the preparation process, the prepared mesoporous TiO2The surface electrical property of the adsorbent is positive, and pollutants with negative electricity can be efficiently adsorbed; when alkaline solution is used in the preparation process, the prepared mesoporous TiO2The surface electrical property of the adsorbent is negative, and pollutants with positive electricity can be efficiently adsorbed. After the adsorption is completed, to the mesoporous TiO2Strong oxidant is added into the adsorbent to oxidize the adsorbed pollutant into harmless CO2And H2O, namely obtaining regenerated mesoporous TiO2The adsorbent can be recycled.
The present invention will be further described with reference to the following examples.
Example 1:
recyclable mesoporous TiO with negative surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 100mL of isopropanol with 25mL of deionized water, adding 5mL of ammonia water into the mixture, and stirring the mixture at room temperature;
2) adding 75mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40h at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:3, and the volume ratio of the ammonia water to the deionized water is 1: 5;
3) centrifuging the obtained suspension at 8000rpm for 10min, washing with deionized water and isopropanol for three times, drying at 80 deg.C for 12 hr, and grinding to obtain TiO2An adsorbent powder.
Prepared by the method of this exampleOf TiO 22Adsorbent, without lattice structure, of amorphous TiO2The transmission electron microscope picture is shown in figure 1, and the Fourier infrared spectrum is shown in figure 2, wherein the Fourier infrared spectrum is located at 1402cm-1The peak is a symmetric stretching vibration peak of carboxylate radical and is positioned at 3434cm-1The peak at (A) is the stretching vibration peak of the hydroxyl group, indicating that the TiO is2The surface of the adsorbent has active functional groups of hydroxyl and carboxyl, so that a large number of active sites are provided for adsorption.
For the prepared TiO2The adsorbent is subjected to specific surface area and pore size analysis tests, and the specific surface area and pore size parameters obtained by the tests are shown in table 1.
TABLE 1 TiO2List of specific surface area and pore size parameters for the adsorbent
BET specific surface area (m)2/g) Average pore diameter (nm) Pore volume (cm)3/g)
421.425 9.536 0.570
As can be seen from Table 1, the TiO produced by this method2The adsorbent has a mesoporous structure, the average pore diameter is 9.536nm, and the BET specific surface area reaches 421.425m2And the adsorption sites are multiple, so that the adsorption of pollutants is facilitated.
TiO produced by zeta potential instrument test2The surface potential of the adsorbent is-40.1 mV, which shows that the surface electric property is negative.
This examplePrepared TiO2The adsorbent is applied to adsorption of a positively charged pollutant methylene blue, and the specific operation is as follows: preparing 10mL methylene blue solution with the concentration of 100mg/L, and weighing TiO2The powder was added to the suspension to a concentration of 0.5g/L, and the suspension was centrifuged after stirring at 25 ℃ for 3 hours in the dark. Measuring the supernatant fluid by using an ultraviolet-visible spectrophotometer at 200-800 nm, and obtaining TiO by calculation2The adsorbing amount of the adsorbent to methylene blue was 189.3 mg/g. Mixing the precipitate with 10mL of sodium hypochlorite solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of 184.2mg/g to methylene blue at the moment, continuously repeating the degradation adsorption to obtain the adsorption quantities of 181.9mg/g, 188.5mg/g and 179.1mg/g in sequence for multiple cycles of the adsorbent, and indicating that the mesoporous TiO is2The adsorbent can be recycled, and the adsorption capacity is not affected in at least five cycles.
The absorption spectrum of the methylene blue solution in the adsorption process is shown in FIG. 3, from which it can be seen that the absorption spectrum passes through TiO2The absorbance of the methylene blue solution after adsorption is reduced to 0, and the adsorption is finished within 20min, which indicates that the TiO is adsorbed2The adsorbent has strong adsorption capacity and high adsorption speed. In addition, such excellent adsorption performance can be more intuitively observed from the comparison of photographs before and after the adsorption of the methylene blue solution in FIG. 3.
Example 2:
recyclable mesoporous TiO with negative surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 50mL of isopropanol with 25mL of deionized water, adding 12.5mL of ammonia water, and stirring at room temperature;
2) adding 25mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40 hours at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 2:1:1, and the volume ratio of the ammonia water to the deionized water is 1: 2;
3) centrifuging the obtained suspensionCentrifuging at 8000rpm for 10min, washing with deionized water and isopropanol for three times, drying at 50 deg.C for 20 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material is rich in active functional groups of hydroxyl and carboxyl, and the specific surface area of the material is 420.266m2The specific surface area is 8.897nm, the specific surface area is-45.2 mV, which indicates that the surface electric property is negative.
The TiO prepared in this example2The adsorbent is applied to adsorption of a pollutant nile blue with positive electricity, and the specific operation is as follows: 10mL of nile blue solution with the concentration of 1mg/L is prepared, and TiO is weighed2The powder was added to the suspension to a concentration of 0.1g/L, and the suspension was centrifuged after stirring at 25 ℃ for 3 hours in the dark. Measuring the supernatant fluid by using an ultraviolet-visible spectrophotometer at 200-800 nm, and obtaining TiO by calculation2The adsorption amount of the adsorbent to nile blue was 175.9 mg/g. Mixing the precipitate with 10mL potassium hypochlorite solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the adsorbent to Nile blue of 169.7mg/g, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
Example 3
Recyclable mesoporous TiO with negative surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 100mL of isopropanol with 25mL of deionized water, adding 2.5mL of ammonia water, and stirring at room temperature;
2) adding 40mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 80 hours at the stirring speed of 100rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:1.6, and the volume ratio of the ammonia water to the deionized water is 1: 10;
3) centrifuging the obtained suspension at 8000rpm for 10min,washing with deionized water and isopropanol for three times, drying at 100 deg.C for 8 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 468.92m2The specific surface area is 7.057nm, the specific surface area is-30.1 mV, which indicates that the surface electric property is negative.
The TiO prepared in this example2The adsorbent is applied to adsorption of positively charged pollutant melamine, and the specific operation is as follows: 10mL of melamine solution with the concentration of 600mg/L is prepared, and TiO is weighed2Adding the powder to the suspension to make the concentration of the powder to be 10g/L, stirring the mixture in the dark at 35 ℃ for 20min, and then centrifuging the suspension. And measuring the supernatant by using an ultraviolet-visible spectrophotometer at 200-800 nm. Obtaining TiO by calculation2The amount of melamine adsorbed by the adsorbent was 87.3 mg/g. Mixing the precipitate with 10mL of potassium persulfate solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the adsorbent to the melamine at the time of calculation to be 91.7mg/g, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
Example 4
Recyclable TiO with negative surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 50mL of isopropanol with 25mL of deionized water, adding 12.5mL of sodium hydroxide solution (the concentration is 0.1mol/L), and stirring at room temperature;
2) adding 25mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 5 hours at the stirring speed of 700rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 2:1:1, and the volume ratio of the sodium hydroxide solution to the deionized water is 1: 2;
3) the resulting suspension was centrifuged at 8000rpm for 10 hoursmin, washing with deionized water and isopropanol for three times, drying at 50 deg.C for 20 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 401.893m2The specific surface area of the material is 11.059nm, the material has a mesoporous structure, and the surface potential of the material is-43.1 mV, which indicates that the surface electrical property of the material is negative.
The TiO prepared in this example2The adsorbent is applied to adsorption of positively charged pollutant basic fuchsin, and the specific operation is as follows: preparing 10mL of basic fuchsin solution with the concentration of 100mg/L, and weighing TiO2Adding the powder to the suspension to make the concentration of the powder 0.5g/L, stirring at 45 deg.C in dark for 20min, and centrifuging the suspension. And measuring the supernatant by using an ultraviolet-visible spectrophotometer at 200-800 nm. Obtaining TiO by calculation2The amount of the adsorbent adsorbed basic fuchsin was 170.9 mg/g. Mixing the precipitate with 10mL of sodium persulfate solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2The adsorbent is used for repeating the previous adsorption operation again, and the adsorption quantity of the adsorbent to the basic fuchsin at the moment is calculated to be 158.7mg/g, which indicates that the mesoporous TiO2The adsorbent can be recycled.
Example 5
Recyclable TiO with negative surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 50mL of isopropanol with 25mL of deionized water, adding 2.5mL of potassium hydroxide solution (the concentration is 1mol/L), and stirring at room temperature;
2) adding 25mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 5 hours at the stirring speed of 700rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 2:1:1, and the volume ratio of the potassium hydroxide solution to the deionized water is 1: 2;
3) centrifuging the obtained suspension at 8000rpmWashing for three times with deionized water and isopropanol, drying at 80 deg.C for 10 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 401.893m2The specific surface area of the material is 11.059nm, the material has a mesoporous structure, and the surface potential of the material is-43.1 mV, which indicates that the surface electrical property of the material is negative.
The TiO prepared in this example2The adsorbent is applied to adsorption of positively charged pollutant doxycycline, and the specific operation is as follows: preparing 10mL doxycycline solution with the concentration of 100mg/L, and weighing TiO2Adding the powder to the suspension to make the concentration of the powder 0.5g/L, stirring at 45 deg.C in dark for 20min, and centrifuging the suspension. And measuring the supernatant by using an ultraviolet-visible spectrophotometer at 200-800 nm. Obtaining TiO by calculation2The adsorption capacity of the adsorbent to doxycycline is 105.1 mg/g. Mixing the precipitate with 10mL of sodium persulfate solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the doxycycline to 102.8mg/g, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
Example 6
Recyclable mesoporous TiO with positive surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 100mL of isopropanol with 25mL of deionized water, adding 12.5mL of hydrochloric acid solution (the concentration is 37 wt%), and stirring at room temperature;
2) adding 75mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40 hours at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:3, and the volume ratio of the hydrochloric acid to the deionized water is 1: 2;
3) centrifuging the obtained suspension at 8000rpmWashing for three times with deionized water and isopropanol, drying at 80 deg.C for 12 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 429.084m2The solution has a mesoporous structure with an average pore diameter of 9.857nm, and the surface potential of the solution is +42.5mV, which indicates that the surface electric property is positive.
The TiO prepared in this example2The adsorbent is applied to adsorption of a pollutant methyl orange with negative electricity, and the specific operation is as follows: preparing 10mL of methyl orange solution with the concentration of 600mg/L, and weighing TiO2Adding the powder into the mixture to enable the concentration of the powder to be 3g/L, stirring the mixture for 2 hours in the dark at the temperature of 25 ℃, then taking suspension for centrifugal separation, and measuring supernatant fluid by using an ultraviolet visible spectrophotometer at the wavelength of 200-800 nm. Obtaining TiO by calculation2The adsorption capacity of the adsorbent to methyl orange is 107.4 mg/g. Mixing the precipitate with 10mL of potassium persulfate solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the adsorbent to methyl orange at the moment of 102.2mg/g, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
Example 7
Recyclable mesoporous TiO with positive surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) 100mL of isopropanol was mixed with 25mL of deionized water, and 2.5mL of hydrochloric acid solution (37 wt% concentration) was added thereto, followed by stirring at room temperature;
2) adding 75mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40 hours at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:3, and the volume ratio of the hydrochloric acid to the deionized water is 1: 10;
3) centrifuging the obtained suspension at 8000rpm for 10min, and repeating the stepsWashing with deionized water and isopropanol for three times, drying at 80 deg.C for 12 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 482.79m2The specific surface area of the mesoporous silicon material is 13.591nm, the mesoporous silicon material has a mesoporous structure, the surface potential of the mesoporous silicon material is +25.8mV, and the surface electric property of the mesoporous silicon material is positive.
The TiO prepared in this example2The adsorbent is applied to adsorption of negative pollutant amaranth, and the specific operation is as follows: preparing 10mL amaranth solution with the concentration of 100mg/L, and weighing TiO2The powder was added to the suspension to a concentration of 0.5g/L, and the suspension was centrifuged after stirring in the dark at 25 ℃ for 2 hours. And measuring the supernatant by using an ultraviolet-visible spectrophotometer at 200-800 nm. Obtaining TiO by calculation2The adsorption capacity of the adsorbent to amaranth is 85.3 mg/g. Mixing the precipitate with 10mL potassium hypochlorite solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption amount of amaranth of 80.1mg/g, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
Example 8
Recyclable mesoporous TiO with positive surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 100mL of isopropanol with 25mL of deionized water, adding 5mL of acetic acid solution (with the concentration of 98 wt%), and stirring at room temperature;
2) adding 75mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40h at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:3, and the volume ratio of the acetic acid to the deionized water is 1: 5;
3) centrifuging the obtained suspension at 8000rpm for 10min, and adding deionized water and isopropyl alcoholWashing with alcohol for three times, drying at 80 deg.C for 12 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 482.79m2The solution has a mesoporous structure with an average pore diameter of 13.591nm, and the surface potential of the solution is +32.8mV, which indicates that the surface electric property is positive.
The TiO prepared in this example2The adsorbent is applied to adsorption of negative pollutant phenol red, and the specific operation is as follows: preparing 10mL of phenol red solution with the concentration of 100mg/L, and weighing TiO2The powder was added to the suspension to a concentration of 0.5g/L, and the suspension was centrifuged after stirring in the dark at 25 ℃ for 2 hours. And measuring the supernatant by using an ultraviolet-visible spectrophotometer at 200-800 nm. Obtaining TiO by calculation2The adsorption amount of the adsorbent to phenol red was 69.3 mg/g. Mixing the precipitate with 10mL of sodium hypochlorite solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the adsorbent to the phenol red at the moment of 68.7mg/g by calculation, which indicates that the mesoporous TiO is2The adsorbent can be recycled, and the adsorption capacity is not influenced basically in the recycling process.
Example 9
Recyclable mesoporous TiO with positive surface electrical property2The preparation method of the adsorbent comprises the following steps:
1) uniformly mixing 100mL of isopropanol with 25mL of deionized water, adding 5mL of sulfuric acid solution (with the concentration of 98 wt%), and stirring at room temperature;
2) adding 75mL of isopropanol solution of diisopropyl di (acetylacetonate) Titanate (TDAA) with the concentration of 10mmol/L into the solution, and continuously stirring for 40h at the stirring speed of 500rpm to obtain suspension, wherein the volume ratio of the isopropanol, the deionized water and the TDAA solution in the solution is 4:1:3, and the volume ratio of the sulfuric acid to the deionized water is 1: 5;
3) the resulting suspension was centrifuged at 8000rpm for 10 hoursmin, washing with deionized water and isopropanol for three times, drying at 80 deg.C for 12 hr, and grinding to obtain TiO2An adsorbent powder.
The TiO prepared in this example2Adsorbent, without lattice structure, of amorphous TiO2The surface of the material has abundant active functional groups of hydroxyl and carboxyl, and the specific surface area reaches 432.79m2The solution has a mesoporous structure with an average pore diameter of 9.591nm, and the surface potential of the solution is +34.3mV, which indicates that the surface electric property is positive.
The TiO prepared in this example2The adsorbent is applied to the adsorption of pollutant methyl red with negative electricity, and the specific operation is as follows: preparing 10mL of methyl red solution with the concentration of 100mg/L, and weighing TiO2Adding the powder into the mixture to enable the concentration of the powder to be 0.5g/L, stirring the mixture in the dark at the temperature of 25 ℃ for 2 hours, then taking suspension for centrifugal separation, and measuring supernatant fluid by using an ultraviolet visible spectrophotometer at the wavelength of 200-800 nm. Obtaining TiO by calculation2The amount of methyl red adsorbed by the adsorbent was 79.3 mg/g. Mixing the precipitate with 10mL of sodium persulfate solution, stirring for 5h, cleaning and drying the precipitate to obtain regenerated TiO2Repeating the previous adsorption operation again to obtain the adsorption quantity of the adsorbent to the methyl red at the moment of 66.7mg/g by calculation, which indicates that the mesoporous TiO is2The adsorbent can be recycled.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (10)

1. Recyclable mesoporous TiO with adjustable surface electrical property2The preparation method of the adsorbent is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing isopropanol and deionized water, adding an acidic solution or an alkaline solution into the mixture, and stirring to obtain a solution I;
(2) adding an isopropanol solution of diisopropyl di (acetylacetonate) titanate into the solution I, uniformly stirring and centrifuging;
(3) washing the precipitate centrifuged in the step (2) with deionized water and isopropanol, drying and grinding to obtain the mesoporous TiO2An adsorbent.
2. The recyclable mesoporous TiO of claim 1 with adjustable surface electrical properties2The preparation method of the adsorbent is characterized by comprising the following steps: the volume ratio of the isopropanol, the deionized water and the isopropanol solution of the diisopropyl di (acetylacetonate) titanate is 2:1: 1-4: 1:3, wherein the concentration of the isopropanol of the diisopropyl di (acetylacetonate) titanate solution is 10 mmol/L.
3. The recyclable mesoporous TiO of claim 1 with adjustable surface electrical properties2The preparation method of the adsorbent is characterized by comprising the following steps: the acid solution is one of hydrochloric acid, acetic acid or sulfuric acid, and the volume ratio of the addition amount of the acid solution to deionized water is 1: 2-1: 10, wherein the concentration of the hydrochloric acid is 37 wt%, the concentration of the acetic acid is 98 wt%, and the concentration of the sulfuric acid is 98 wt%; the alkaline solution is one of ammonia water, sodium hydroxide or potassium hydroxide solution, the volume ratio of the addition amount of the alkaline solution to the deionized water is 1: 2-1: 10, wherein the concentration of the ammonia water is 25-28 wt%, the concentration of the sodium hydroxide solution is 0.1-1 mol/L, and the concentration of the potassium hydroxide is 0.1-1 mol/L.
4. Recyclable mesoporous TiO with adjustable surface electrical property prepared by the method of any one of claims 1-32Adsorbent of the TiO2The adsorbent is amorphous TiO2And has a mesoporous structure.
5. The recyclable mesoporous TiO with adjustable surface electrical property as claimed in claim 42An adsorbent characterized by: TiO produced when using acidic solutions in the preparation process2TiO produced by using alkaline solution with positive surface electrical property of adsorbent2The surface electrical property of the adsorbent is negative.
6. The method of4 or 5 the mesoporous TiO with the adjustable surface electric property and the recycling property2Use of an adsorbent for adsorbing a positively or negatively charged contaminant.
7. Use according to claim 6, characterized in that: the mesoporous TiO is mixed2The adsorbent is directly mixed with the solution containing the pollutants, and after stirring, solid powder is centrifugally separated.
8. Use according to claim 6, characterized in that: the initial concentration of the solution containing the pollutants is 1-600 mg/L, and TiO is2The addition amount of the adsorbent is 0.1-10 g/L, the adsorption time is 20 min-3 h, and the adsorption temperature is 25-45 ℃.
9. Use according to claim 6, characterized in that: after the adsorption process, the separated TiO is centrifuged2Adding strong oxidant into the adsorbent to degrade the adsorbed pollutant to obtain regenerated mesoporous TiO2The adsorbent can be recycled.
10. Use according to claim 9, characterized in that: the strong oxidant is one of potassium persulfate, sodium persulfate, potassium hypochlorite and sodium hypochlorite.
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