Preparation and application of silver-modified spiral titanium dioxide nano-fiber photocatalyst

Abstract

The present invention discloses a preparation method of a silver-modified spiral Titanium Dioxide (TiO.sub.2) nano-fiber photocatalyst, comprising the following steps: preparing a spiral TiO.sub.2 nano-fiber; preparing a nano-silver aqueous solution; and preparing a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst. The photocatalyst is coupled with the spiral structure of the nano-fiber and nano-silver particles with a specific size, improving the photocatalytic activity of the photocatalyst. Moreover, the sterilizing and biological pollution resisting capacities of the photocatalyst are also improved through the modified nano-silver particles, and therefore, the photocatalyst can be widely applied to a deep sewage treatment system.

Claims

1. A preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst, comprising the following steps: S1. preparing a spiral TiO.sub.2 nano-fiber: transcribing the structure of amino acid derivatives to prepare the spiral TiO.sub.2 nano-fiber; S2. preparing a nano-silver aqueous solution: preparing the stable nano-silver aqueous solution with a uniform particle size based on a Tollens reaction; and S3. preparing a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst: modifying the nano-silver particles prepared in step S2 onto the spiral TiO.sub.2 nano-fiber prepared in step S1 by using a chemical deposition method, wherein, specific operations of step S1 are: weighing 0.10-0.15 g of C.sub.18-D-glutamic acid to be dissolved in 45.3-68.0 g of methanol solution, adding 270-400 mL of deionized water, and stirring at the room temperature for 10 min to prepare a mixed solution; then weighing 0.97-1.45 g of bis(2,4-pentanedionate)bis(2-pyruvate)titanium to be added in the mixed solution, stirring at 55 C. for 2 hours to obtain an intermediate product; centrifugally separating the obtained intermediate product, freezing and drying at 60 C. overnight to obtain a light yellow powder; and calcining the light yellow powder at 550 C. for 6 hours to obtain a white powder, the white powder being the spiral TiO.sub.2 nano-fiber.

2. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 1, wherein, an average length of the prepared spiral TiO.sub.2 nano-fiber is about 500 nm, and an average diameter thereof is about 40 nm.

3. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 1, wherein, specific operations of step S2 are: mixing a silver nitrate solution with the mass fraction of 24-30% and ammonium hydroxide with the mass fraction of 28-34% to prepare reagent A, mixing a sodium hydroxide solution with the mass fraction of 7-12% and ammonium hydroxide with the mass fraction of 6-10% to prepare reagent B, and mixing formaldehyde with the mass fraction of 0.3% and sorbitol with the mass fraction of 27-33% to prepare reagent C; adding 0.5 mL of the reagent A to 14 mL of deionized water, adding 0.5 mL of the reagent B, and filling to volume of 300 mL to prepare reagent SAB; individually filling 0.5 mL of the reagent C to volume of 300 mL to prepare reagent SC; and mixing 0.9 mL of the reagent SAB and 0.9 mL of the reagent SC with 10 mL of water, sealing and placing in a numerical control ultrasonic vibrator for ultrasonic vibration to obtain the nano-silver particle aqueous solution.

4. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 3, wherein, the ultrasonic vibration times are 15 min, 27 min, and 33 min to obtain three nano-silver particle aqueous solutions with different sizes.

5. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 4, wherein, the particle diameters of the nano-silver particles are a small size of 4-6 nm, a middle size of 12-14 nm, and a large size of 30-32 nm, respectively corresponding to the three different ultrasonic vibration times.

6. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 5, wherein, specific operations of step S3 are: weighing three parts of 0.2 g of silver-modified spiral TiO.sub.2 nano-fibers prepared in step S1, and respectively dissolving in three kinds of 100 mL, nano-silver aqueous solutions prepared in step S2; adjusting pH of three mixtures to 3.5 with perchloric acid, stirring at the room temperature for 60 min, and then continuously stirring for 40 min at a nitrogen atmosphere under irradiation of a 8 W ultraviolet lamp; and centrifugally separating a product, washing the product multiple times with double-distilled water, and finally drying at 80 C. for 8 hours to obtain three parts of brown powders with different chromaticity, i.e., small-sized, middle-sized, and large-sized nano-silver particle-modified spiral TiO.sub.2 nano-fibers.

7. The preparation method of a silver-modified spiral TiO.sub.2 nano-fiber photocatalyst according to claim 6, wherein, the capacities of nano-silvers with different sizes are 3.3%, 3.1%, and 3.1%, respectively according to the sizes in an ascending order.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a Scanning Electron Microscope (SEM) diagram of a photocatalyst obtained by the preparation method of the present invention, wherein a is a pure spiral TiO.sub.2 nano-fiber, b is a small-sized nano-silver-modified spiral TiO.sub.2 nano-fiber, c, is a middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber, and d is a large-sized nano-silver-modified spiral TiO.sub.2 nano-fiber;

(2) FIG. 2 is a Photoelectron Spectroscopy (XPS) diagram of the middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber photocatalyst, wherein e is a full spectrum, and f is a high power spectrum;

(3) FIG. 3 is a comparison diagram of the removal effect of four photocatalysts to EE2;

(4) FIG. 4 is a comparison diagram of the removal effect of the middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber photocatalyst when being reused to EE2; and

(5) FIG. 5 is a comparison diagram of the removal effect of the pure spiral TiO.sub.2 nano-fiber photocatalyst and the middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber photocatalyst when being reused to Escherichia coli.

DETAILED DESCRIPTION

(6) The prevent invention is specifically introduced with a combination of the accompanying drawings and the specific embodiments.

(7) All raw materials are purchased in markets, unless otherwise described in the present invention.

Embodiment 1-1

(8) This embodiment prepares a pure spiral TiO.sub.2 nano-fiber, and the preparation process is as follows:

(9) weighing 0.12 g of Ca-D-glutamic acid to be dissolved in 54.4 g of methanol solution, adding 320 mL of deionized water, and stirring at the room temperature for 10 min to prepare a mixed solution; then weighing 1.16 g of bis(2,4-pentanedionate)bis(2-pyruvate)titanium to be added in the mixed solution, stirring at 55 C. for 2 hours to obtain an intermediate product; centrifugally separating the obtained intermediate product, freezing and drying at 60 C. overnight to obtain a light yellow powder; calcining the light yellow powder at 550 C. for 6 hours to obtain a white powder, the white powder being the spiral TiO.sub.2 nano-fiber.

(10) Upon detection, the average length of the pure spiral TiO.sub.2 nano-fiber photocatalyst prepared in this embodiment is about 500 nm, and the average diameter thereof is about 40 nm.

Embodiment 1-2

(11) This embodiment prepares a pure spiral TiO.sub.2 nano-fiber, and the preparation process is as follows:

(12) weighing 0.10 g of C.sub.18-D-glutamic acid to be dissolved in 45.3 g of methanol solution, adding 270 mL of deionized water, and stirring at the room temperature for 10 min to prepare a mixed solution; then weighing 0.97 g of bis(2,4-pentanedionate)bis(2-pyruvate)titanium to be added in the mixed solution, stirring at 55 C. for 2 hours to obtain an intermediate product; centrifugally separating the obtained intermediate product, freezing and drying at 60 C. overnight to obtain a light yellow powder; calcining the light yellow powder at 550 C. for 6 hours to obtain a white powder, the white powder being the spiral TiO.sub.2 nano-fiber.

(13) Upon detection, the average length of the pure spiral TiO.sub.2 nano-fiber photocatalyst prepared in this embodiment is about 500 nm, and the average diameter thereof is about 40 nm.

Embodiment 1-3

(14) This embodiment prepares a pure spiral TiO.sub.2 nano-fiber, and the preparation process is as follows:

(15) weighing 0.15 g of C.sub.18-D-glutamic acid to be dissolved in 68.0 g of methanol solution, adding 400 mL of deionized water, and stirring at the room temperature for 10 min to prepare a mixed solution; then weighing 1.45 g of bis(2,4-pentanedionate)bis(2-pyruvate)titanium to be added in the mixed solution, stirring at 55 C. for 2 hours to obtain an intermediate product; centrifugally separating the obtained intermediate product, freezing and drying at 60 C. overnight to obtain a light yellow powder; calcining the light yellow powder at 550 C. for 6 hours to obtain a white powder, the white powder being the spiral TiO.sub.2 nano-fiber.

(16) Upon detection, the average length of the pure spiral TiO.sub.2 nano-fiber photocatalyst prepared in this embodiment is about 500 nm, and the average diameter thereof is about 40 nm.

Embodiment 2

(17) The stable and small-sized (4-6 nm) nano-silver aqueous solution is prepared based on the Tollens reaction:

(18) the specific operation process comprises: mixing a silver nitrate solution with the mass fraction of 24-30% and ammonium hydroxide with the mass fraction of 28-34% to prepare reagent A, mixing a sodium hydroxide solution with the mass fraction of 7-12% and ammonium hydroxide with the mass fraction of 6-10% to prepare reagent B, and mixing formaldehyde with the mass fraction of 0.3% and sorbitol with the mass fraction of 27-33% to prepare reagent C; adding 0.5 mL of the reagent A to 14 mL of deionized water, adding 0.5 mL of the reagent B, and filling to volume of 300 mL to prepare reagent SAB; individually filling 0.5 mL of the reagent C to volume of 300 mL to prepare reagent SC; and mixing 0.9 mL of the reagent SAB and 0.9 mL of the reagent SC with 10 mL of water, sealing and placing in a numerical control ultrasonic vibrator for ultrasonic vibration for 15 min to obtain the small-sized (4-6 nm) nano-silver particle aqueous solution.

(19) Then the small-sized nano-silver particles prepared in this embodiment are modified onto the spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1 by using a chemical deposition method:

(20) the specific operation process comprises: weighing 0.2 g of spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1, and dissolving in 100 mL nano-silver aqueous solutions prepared in this embodiment; adjusting pH of the mixture to 3.5 with perchloric acid, stirring at the room temperature for 60 min, and then continuously stirring for 40 min at a nitrogen atmosphere under irradiation of a 8 W ultraviolet lamp; and centrifugally separating a product, washing the product multiple times with double-distilled water, and finally drying at 80 C. for 8 hours to obtain brown powders, i.e., small-sized (4-6 nm) nano-silver particle-modified spiral TiO.sub.2 nano-fibers, wherein the capacity of nano-silver is 3.3%.

Embodiment 3

(21) The stable and middle-sized (12-14 nm) nano-silver aqueous solution is prepared based on the Tollens reaction:

(22) the specific operation process comprises: mixing a silver nitrate solution with the mass fraction of 24-30% and ammonium hydroxide with the mass fraction of 28-34% to prepare reagent A, mixing a sodium hydroxide solution with the mass fraction of 7-12% and ammonium hydroxide with the mass fraction of 6-10% to prepare reagent B, and mixing formaldehyde with the mass fraction of 0.3% and sorbitol with the mass fraction of 27-33% to prepare reagent C; adding 0.5 mL of the reagent A to 14 mL of deionized water, adding 0.5 mL of the reagent B, and filling to volume of 300 mL to prepare reagent SAB; individually filling 0.5 mL of the reagent C to volume of 300 mL to prepare reagent SC; and mixing 0.9 mL of the reagent SAB and 0.9 mL of the reagent SC with 10 mL of water, sealing and placing in a numerical control ultrasonic vibrator for ultrasonic vibration for 27 min to obtain the middle-sized (12-14 nm) nano-silver particle aqueous solution.

(23) Then the middle-sized nano-silver particles prepared in this embodiment are modified onto the spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1 by using a chemical deposition method:

(24) the specific operation process comprises: weighing 0.2 g of spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1, and dissolving in 100 mL nano-silver aqueous solutions prepared in this embodiment; adjusting pH of the mixture to 3.5 with perchloric acid, stirring at the room temperature for 60 min, and then continuously stirring for 40 min at a nitrogen atmosphere under irradiation of a 8 W ultraviolet lamp; and centrifugally separating a product, washing the product multiple times with double-distilled water, and finally drying at 80 C. for 8 hours to obtain brown powders, i.e., middle-sized (12-14 nm) nano-silver particle-modified spiral TiO.sub.2 nano-fibers, wherein the capacity of nano-silver is 3.1%.

Embodiment 4

(25) The stable and large-sized (30-32 nm) nano-silver aqueous solution is prepared based on the Tollens reaction:

(26) the specific operation process comprises: mixing a silver nitrate solution with the mass fraction of 24-30% and ammonium hydroxide with the mass fraction of 28-34% to prepare reagent A, mixing a sodium hydroxide solution with the mass fraction of 7-12% and ammonium hydroxide with the mass fraction of 6-10% to prepare reagent B, and mixing formaldehyde with the mass fraction of 0.3% and sorbitol with the mass fraction of 27-33% to prepare reagent C; adding 0.5 mL of the reagent A to 14 mL of deionized water, adding 0.5 mL of the reagent B, and filling to volume of 300 mL to prepare reagent SAB; individually filling 0.5 mL of the reagent C to volume of 300 mL to prepare reagent SC; and mixing 0.9 mL of the reagent SAB and 0.9 mL of the reagent SC with 10 mL of water, sealing and placing in a numerical control ultrasonic vibrator for ultrasonic vibration for 33 min to obtain the large-sized (30-32 nm) nano-silver particle aqueous solution.

(27) Then the large-sized nano-silver particles prepared in this embodiment are modified onto the spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1 by using a chemical deposition method:

(28) the specific operation process comprises: weighing 0.2 g of spiral TiO.sub.2 nano-fiber prepared in embodiment 1-1, and dissolving in 100 mL nano-silver aqueous solutions prepared in this embodiment; adjusting pH of the mixture to 3.5 with perchloric acid, stirring at the room temperature for 60 min, and then continuously stirring for 40 min at a nitrogen atmosphere under irradiation of a 8 W ultraviolet lamp; and centrifugally separating a product, washing the product multiple times with double-distilled water, and finally drying at 80 C. for 8 hours to obtain brown powders, i.e., large-sized (30-32 nm) nano-silver particle-modified spiral TiO.sub.2 nano-fibers, wherein the capacity of nano-silver is 3.1%.

(29) Morphology Detection

(30) Embodiments 1-4 prepare the pure spiral TiO.sub.2 nano-fiber, the small-sized nano-silver particle-modified spiral TiO.sub.2 nano-fiber, the middle-sized nano-silver particle-modified spiral TiO.sub.2 nano-fiber, and the large-sized nano-silver particle-modified spiral TiO.sub.2 nano-fiber, respectively. Please refer to FIG. 1 for the SEM diagram of each product. It can be seen from FIG. 1 that the average length of the silver-modified spiral TiO.sub.2 nano-fiber photocatalyst is about 500 nm, and the average diameter thereof is about 40 nm. Deposition of the nano-silver particles does not destroy the spiral structure of the TiO.sub.2 nano-fiber, and the average particle diameters of the nano-silver particles of three sizes are 4-6 nm (small size), 12-14 nm (middle size), and 30-32 nm (large size), respectively.

(31) FIG. 2 is an XPS diagram of the middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber photocatalyst prepared in embodiment 2, wherein e is a full spectrum, and f is a high power spectrum. It can be seen from FIG. 2e that no other impurity element appears apart from a small number of carbon comprised in the XPS device. It can be seen from FIG. 2f that the modified nano-silver particles mainly exist in an elementary substance form.

(32) Performance Detection

(33) (1). A photocatalytic degradation effect of the visible light photocatalyst of embodiments 1-4 to a pollutant in water, i.e., EE2:

(34) Implementation conditions: a degradation reaction is conducted in a glass beaker, and the light source is a xenon arc lamp (300 W) provided with an ultraviolet filter which can provide visible light irradiation (the wavelength is greater than 400 nm).

(35) Implementation process: weighing 0.5 mg of EE2 to be added in 100 mL of double-distilled water, then adding 0.1 g of ethanol to promote dissolution of EE2, and finally adding 0.1 g of photocatalyst. First, a reaction system is placed in a dark condition and stirred for 30 min to achieve adsorption desorption equilibrium of EE2. Then the xenon arc lamp is turned on to start a photocatalytic degradation reaction; the reaction lasts for one hour, 0.5 mL of water sample is taken every 10 min, and three repeated water samples are taken each time; after the photocatalyst is removed through centrifugation, the concentration of EE2 in the water samples is measured with a high performance liquid chromatograph, and all values are average values of three repeated water samples.

(36) FIG. 3 shows the experimental results of embodiments 1-4. The results indicate that: the pure spiral TiO.sub.2 nano-fiber photocatalyst in embodiment 1-1 only degrades 19% of EE2. However, three silver-modified spiral TiO.sub.2 nano-fiber photocatalyst in embodiments 2-4 degrade 85%, 100%, and 80% of EE2, respectively, i.e., the optimal particle diameter of modified nano-silver particle is 12-14 nm (middle size).

(37) (2). The middle-sized silver-modified photocatalyst is reused by using an extraction filtration washing method, and after being cycled by five times, the degradation efficiency of the photocatalyst to EE2 is not obviously reduced. Please refer to FIG. 4 for the detection result.

(38) (3). The inactivation effect of the pure spiral TiO.sub.2 nano-fiber photocatalyst and the middle-sized nano-silver-modified spiral TiO.sub.2 nano-fiber photocatalyst when being reused to Escherichia coli:

(39) multiplying Escherichia coli with a tryptone soybean broth medium, centrifuging the Escherichia coli after it enters a logarithmic phase at a shaking table of 37 C., discarding a supernatant, and washing with a phosphate buffer solution; centrifugally washing multiple times and then suspending the Escherichia coli in sterilized saline water (the mass fraction of NaCl is 0.9%), and adjusting pH to about 7 to finally obtain an Escherichia coli suspension with the concentration of about 110.sup.7 cfu/mL.

(40) 0.1 g of photocatalyst is weighed to be added in 100 mL of Escherichia coli suspension, the xenon arc lamp is then turned on for continuous inactivation for 30 min, and finally three repeated water samples are taken to measure the average concentration of Escherichia coli. The water samples needs to be first diluted to a suitable concentration, and then agar plate count of Escherichia coli is conducted, all values are average values of three repeated water samples.

(41) With reference to FIG. 5, the results of embodiments 11 and 3 indicate that the removal of Escherichia coli by the pure spiral TiO.sub.2 nano-fiber photocatalyst is only level-2 logarithmic removal rate (2-log), while the removal of Escherichia coli by the middle-sized silver-modified TiO.sub.2 nano-fiber photocatalyst can reach level-7 logarithmic removal rate (7-log). After being cycled for five times, the removal efficiency of the two photocatalysts to Escherichia coli is not obviously reduced.

(42) In conclusion, the TiO.sub.2 photocatalyst obtained by the preparation method of the present invention is coupled with the spiral structure of the nano-fiber and nano-silver particles with a specific size, exciting the SPR effect through resonance to the maximum extent, promoting the photocatalytic activity of the photocatalyst, improving absorption of the photocatalyst to the visible light, and moreover, also increasing the sterilizing and biological pollution resisting capacities of the material. The middle-sized nano-silver particle-modified TiO.sub.2 nano-fiber photocatalyst has the strongest activity and the best degradation effect. In addition, the visible light photocatalyst of the present invention can be reused, and the efficiency fox degradation of organic pollutants and inactivation of pathogenic bacteria is not obviously reduced.

(43) The contents above display and describe fundamental principles, main characteristics, and advantages of the present invention. A person of ordinary skill in the art shall understand that the aforementioned embodiments do not limit the present invention in any form, and the technical solutions obtained through equivalent substitution or equivalent transformation all fall within the scope of protection of the present invention.