CN112973686A - Method for enhancing photocatalytic performance of heterostructure composite material through pyroelectric effect and application - Google Patents
Method for enhancing photocatalytic performance of heterostructure composite material through pyroelectric effect and application Download PDFInfo
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 4
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Abstract
The invention discloses a method for enhancing the photocatalytic performance of a heterostructure composite material by using a pyroelectric effect and application thereof. With Ba (CH)3COO)2、Sr(CH3COO)2And tetrabutyl titanate as raw material, according to Ba1‑xSrxTiO3(x is more than or equal to 0 and less than or equal to 1), forming stable sol through hydrolysis and polycondensation, gradually converting the sol into wet gel, and preparing the wet gel into hollow Ba through electrostatic spinning and calcining methods1‑xSrxTiO3Nanotubes and silver by ion adsorptionNanoparticles and silver oxide particles attached to Ba1‑xSrxTiO3Centrifuging, drying and heat treating the nano tube to obtain an S-type or Z-type heterostructure composite material Ba1‑xSrxTiO3/Ag/Ag2And O. The preparation method has the advantages of simple process and flow, wide parameter adjustable range and strong repeatability, and has commercial prospect. Using Ba1‑ xSrxTiO3The generated pyroelectric effect enhances the photocatalytic efficiency of the prepared heterostructure composite material, and has important application value in the fields of photocatalytic sterilization, polysaccharide degradation, organic pollutant degradation, heavy metal ion reduction and the like.
Description
Technical Field
The invention belongs to the field of photocatalysis, and relates to a method for achieving catalytic oxidation and reduction by means of solar energy and achieving the effect of enhancing photocatalysis by utilizing the pyroelectric effect.
Background
Photocatalysis is a technology with low energy consumption, high efficiency and no secondary pollution, is concerned about because of the advantages of mild reaction conditions and capability of directly converting solar energy into chemical energy, and is widely applied to the fields of pollutant degradation, water decomposition for hydrogen production, carbon dioxide reduction and the like. However, the traditional catalyst has three problems at present, namely (1) the electron/hole recombination speed is high, which causes the performance of the material to be reduced; (2) the absorption amount of visible light is low, and the application of the visible light is restricted from technical utilization and resources; (3) the photocatalyst has low surface coverage, resulting in a low degradation rate of organic contaminants.
Currently, photocatalytic performance can be improved by doping ions (including cations or anions) or coupling with other semiconductor photocatalysts to expand the light absorption in the visible region of the spectrum. Many researches for enhancing the photocatalytic activity of solar energy by using solar energy, such as CuO/Ag2O、Ag2O/ZnO、Ag2O/Ag2S and the like. However, there are still significant drawbacks in terms of catalytic efficiency, since the effect is solely dependent on solar energy and only responds to the ultraviolet and visible part of the sunlight.
Disclosure of Invention
The invention aims to provide a method for enhancing the photocatalytic performance of a heterostructure composite material by using a pyroelectric effect, which is used for enhancing the photocatalytic performance of the heterostructure composite material and carrying out photocatalytic oxidation, reduction and other applications.
The invention utilizes Ba1-xSrxTiO3The pyroelectric effect enhances the photocatalytic performance of the heterostructure composite material, and the heterostructure composite material is: ba1-xSrxTiO3/Ag/Ag2O(0≤x≤1)。
The complete technical scheme of the invention is as follows: a method for enhancing the photocatalytic performance of a heterostructure composite material by a pyroelectric effect comprises the following steps:
a. according to Ba1-xSrxTiO3(x is more than or equal to 0 and less than or equal to 1) in a stoichiometric ratio, and dissolving barium acetate and strontium acetate in a solvent to obtain a solution A; adding tetrabutyl titanate into the solution A to obtain a solution B, and carrying out hydrolysis and condensation reactions to obtain Ba1-xSrxTiO3Wet gel; calcining to obtain Ba1-xSrxTiO3A xerogel;
b. ba obtained from a1-xSrxTiO3Grinding the dry gel into powder, adding a solvent to prepare a precursor solution, and spinning into Ba by an electrostatic spinning method1-xSrxTiO3The nano-fiber is put into a muffle furnace to be calcined to obtain Ba1-xSrxTiO3A nanotube;
c. ba obtained by b1-xSrxTiO3Weighing 1mmol of nanotube, and adding AgNO with a certain concentration3In the solution, the pH value is adjusted by 0.2mol/L sodium hydroxide solution to lead the Ag to be2O attachment to Ba1-xSrxTiO3Nanotube to obtain Ba1-xSrxTiO3/Ag2An O composite heterostructure;
d. ba obtained by the above c1-xSrxTiO3/Ag2Irradiating the O suspension under an ultraviolet lamp for a period of time to obtain Ba1- xSrxTiO3/Ag/Ag2Removing supernatant from suspension O, washing the precipitate with deionized water and ethanol for 3 times, centrifuging, and drying in oven at 60 deg.C for 24 hr to obtain Ba1-xSrxTiO3/Ag/Ag2An O-heterostructure composite catalyst.
The solvent in the step a is deionized water, and the added volume is 10mL-30 mL.
The temperature of the muffle furnace calcination in the step a is 300-800 ℃.
The solvent used in the preparation of the precursor solution by the electrospinning method in the step b comprises polyvinylpyrrolidone (PVP) and Dimethylformamide (DMF).
The calcining temperature in the step b is 500-800 ℃.
AgNO in step c3Has a concentration of 0.1mol/L to 1mol/L
The adjusted pH in step c is in the range of 11-13.
In the step d, the irradiation time of the ultraviolet lamp is 10min-60min, and the irradiation distance is 5cm-10 cm.
Ba in step d1-xSrxTiO3/Ag/Ag2O heterostructure composite catalyst of Ba1-xSrxTiO3Has pyroelectric effect and can enhance the photocatalytic performance.
Ba in step d1-xSrxTiO3/Ag/Ag2O constitutes an S-type or Z-type heterostructure.
Compared with the prior art, the invention has the following excellent characteristics:
(1) the advantages of the pyroelectric effect are utilized to enhance the photocatalytic performance of the heterostructure composite material, and good photocatalytic performance enhancement is realized.
(2) The specific surface area of the heterogeneous composite structure catalyst is greatly improved, and the Ag is carried by the hollow nanotube made of Ba1-xSrxTiO32The O nanoparticles allow for efficient contact with contaminants and the like.
(3) Constructing novel S-type or Z-type Ba1-xSrxTiO3The heterogeneous composite structure greatly reduces the recombination of electron hole pairs, widens the spectral response range to a near infrared light region, and improves the photocatalytic efficiency.
(4) Simple process and flow, short reaction time, adjustable parameters, wide range, strong repeatability and convenient realization of industrial production.
(5) Compared with the traditional photocatalyst, the method introduces a pyroelectric effect to enhance the transfer of internal electrons, and greatly improves the efficiency of realizing photocatalysis by singly depending on solar energy. The catalytic efficiency of the catalyst to the active brilliant red within 20min reaches 100 percent.
Drawings
Fig. 1 SEM image of the heterostructure-composite catalyst prepared in example 1 of the present invention.
Fig. 2 TEM image of the heterostructure composite catalyst prepared in example 1 of the present invention.
Figure 3 XPS spectra of the heterostructure-composite catalyst prepared in example 1 of the present invention.
FIG. 4 is a graph of the efficiency of pyroelectric catalytic degradation of the heterostructure composite prepared in example 2 of the present invention.
FIG. 5 is a graph of the photocatalytic degradation efficiency of the heterostructure composite prepared in example 2 of the present invention.
FIG. 6 is a graph of the efficiency of the pyroelectric electro-optic catalysis synergistic catalytic degradation of the heterostructure composite prepared in example 2 of the present invention.
FIG. 7 is a graph of specific surface area (BSA) of the heterostructure-composite catalyst prepared in example 1 of the present invention.
Detailed Description
The invention utilizes Ba (CH)3COO)2、Sr(CH3COO)2And tetrabutyl titanate as raw material, according to Ba1-xSrxTiO3(x is more than or equal to 0 and less than or equal to 1), forming stable sol through hydrolysis and polycondensation, gradually converting the sol into wet gel, preparing the wet gel into a hollow nanotube through electrostatic spinning and calcining methods, attaching silver nanoparticles and silver oxide particles to the nanotube through an ion adsorption method, centrifuging, drying and carrying out heat treatment to obtain a heterostructure material Ba1-xSrxTiO3/Ag/Ag2And O. Using Ba1-xSrxTiO3The generated pyroelectric effect is used for enhancing the photocatalytic performance of the heterostructure composite material, and is applied to photocatalytic sterilization, polysaccharide degradation and the like.
The specific process flow is as follows:
(1) preparation of Ba by sol-gel method0.6Sr0.4TiO3Precursor solution of Ba (CH)3COO)2、Sr(CH3COO)2Respectively dissolving with tetrabutyl titanate, hydrolyzing, polycondensing to form stable sol, gradually converting into wet gel, and preparing Ba by electrostatic spinning0.6Sr0.4TiO3Calcining the prepared nano-fiber in a 800-degree muffle furnace for 3 hours to obtain Ba0.6Sr0.4TiO3Hollow nanotubes.
(2) Weighing 1mmol of Ba0.6Sr0.4TiO3The nanotube is added with 10ml of deionized water and fully stirred, and silver nitrate solutions of 0.1mol/L, 0.2mol/L and 0.3mol/L are respectively weighed. Stirring until it is sufficiently dissolved, and dropping 1mmol of Ba0.6Sr0.4TiO3Adjusting pH to 12.64 with 0.2mol/L sodium hydroxide solution, stirring for 60min with a magnetic stirrer, irradiating with ultraviolet light for 20min, removing supernatant, washing precipitate with deionized water and ethanol for 3 times, and drying in an oven at 60 deg.C for 24 hr to obtain Ba0.6Sr0.4TiO3:Ag2The composite material with O of 1:0.5, 1:1 and 1:2 is named as BST/Ag2O-0.5、BST/Ag/Ag2O-1、BST/Ag/Ag2O-1.5。
Example 1:
(1) 1.53g of Ba (CH)3COO)2And 0.584g of Sr (CH)3COO)2And 5ml of tetrabutyl titanate are dissolved in 20ml of deionized water, and the wet gel is generated through hydrolysis and condensation. Then preparing Ba by electrostatic spinning method0.6Sr0.4TiO3Calcining the prepared nano-fiber in a 800-degree muffle furnace for 3 hours to obtain Ba0.6Sr0.4TiO3Hollow nanotubes.
(2) 1mmol of Ba is taken0.6Sr0.4TiO3The nano-tube is put into 0.2mol/L silver nitrate solution to be evenly stirred for 20 minutes, and then the pH value is adjusted to 12.64 by 0.2mol/L NaOH solution to obtain Ba0.6Sr0.4TiO3/Ag2O composite material, which was then moved to an ultraviolet lamp and irradiated for 20 minutes to obtain Ba0.6Sr0.4TiO3/Ag/Ag2And (3) an O catalyst. When the catalyst is used for killing escherichia coli, intracellular coenzyme A is oxidized into dimeric coenzyme A, so that cell respiration is reduced and death is caused.
As shown in fig. 1 and 2, SEM images and TEM images of the heterostructure composite catalyst showed that the catalyst was present in Ba0.6Sr0.4TiO3Ag nanoparticles and Ag were successfully attached to the nanotubes2And (4) O particles. FIG. 3 shows Ba tested by XPS0.6Sr0.4TiO3/Ag/Ag2Chemical elements and chemical environment in the O composite. The complete XPS spectrum given in FIG. 3(a) clearly shows the presence of Ba, Sr, Ti, Ag and O elements in the sample. In FIG. 3(e), the peak of Ag-3d includes Ag0And Ag+Indicating that Ag exhibits an oxidation state of Ag + and elemental silver. As shown in fig. 7, the specific surface area of the catalyst with the heterogeneous composite structure prepared by the above embodiment is greatly increased.
Example 2:
(1) 1.53g of Ba (CH)3COO)2And 0.584g of Sr (CH)3COO)2Dissolving tetrabutyl titanate 5ml in deionized water 20ml, hydrolyzing, condensing to obtain wet gel,then preparing Ba by electrostatic spinning method0.6Sr0.4TiO3Calcining the prepared nano-fiber in a 800-degree muffle furnace for 3 hours to obtain Ba0.6Sr0.4TiO3Hollow nanotubes.
(2) 1mmol of Ba is taken0.6Sr0.4TiO3The nano-tube is put into 0.3mol/L silver nitrate solution to be evenly stirred for 20 minutes, and then the pH value is adjusted to 12.64 by 0.2mol/L NaOH solution to obtain Ba0.6Sr0.4TiO3/Ag2O, which was subsequently placed under an ultraviolet lamp for 20 minutes to obtain Ba0.6Sr0.4TiO3/Ag/Ag2And (3) an O catalyst.
The obtained heterostructure composite material catalyst is used for degrading organic pollutant active bright red-xb (Rbr-xb). Photocatalytic degradation was accomplished by three experiments. The first experiment was pyroelectric catalysis, as shown in FIG. 4, 0.05g of catalyst was added to 100mL of 5mg/L Rbr-xb solution in the absence of light, stirred well for 1h to reach adsorption equilibrium, and the circulating cold and hot water was changed between 25 deg.C and 60 deg.C by a magnetic stirrer in a heated water bath. 3ml of the Rbr-xb solution are taken out every 5 cycles and after centrifugation the supernatant is extracted and its absorbance at 510nm is measured in a visible spectrophotometer. The second experiment is photocatalysis, as shown in fig. 5, no cold and hot circulating water is introduced, the other conditions are kept unchanged under the irradiation of visible light, 3mL of solution is taken out at intervals of 10 minutes for centrifugal treatment, and then the absorbance at 510nm is measured. Finally, in the case where light and cold and hot circulating water were added simultaneously as shown in fig. 6, 3mL of the solution was taken out at the same time as above, and the absorbance at 510nm was measured. According to the formula eta ═ (C)0-Ct)/C0X 100%, the degradation rate of Rbr-xb, where C0As initial concentration, CtTo take out the concentration of the sample.
Through comparison of three groups of experiments, when only cooling circulating water is used, namely only pyroelectric catalysis is performed, the degradation efficiency of the Rbr-xb after 42 cold and hot cycles is 77%, when the catalytic efficiency is 92% in 50 minutes under the irradiation of visible light, and when the pyroelectric electrocatalysis performed in a synergistic mode, namely after 30min of illumination, 25 times of cooling circulating water is passed in the time, and the degradation rate of the Rbr-xb reaches 100%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for enhancing the photocatalytic performance of a heterostructure composite material by a pyroelectric effect is characterized in that the heterostructure composite material is Ba1-xSrxTiO3/Ag/Ag2O (x is more than or equal to 0 and less than or equal to 1), and the preparation steps are as follows:
a. according to Ba1-xSrxTiO3(x is more than or equal to 0 and less than or equal to 1) in a stoichiometric ratio, and dissolving barium acetate and strontium acetate in a solvent to obtain a solution A; adding tetrabutyl titanate into the solution A to obtain a solution B, and carrying out hydrolysis and condensation reactions to obtain Ba1-xSrxTiO3Wet gel; calcining to obtain Ba1-xSrxTiO3A xerogel;
b. the Ba obtained in the step a is added1-xSrxTiO3Grinding the dry gel into powder, adding a solvent to prepare a precursor solution, and spinning into Ba by an electrostatic spinning method1-xSrxTiO3The nano-fiber is put into a muffle furnace to be calcined to obtain Ba1-xSrxTiO3A nanotube;
c. the Ba obtained in the step b is1-xSrxTiO3Weighing 1mmol of nanotube, and adding AgNO with a certain concentration3In the solution, the pH value is adjusted by 0.2mol/L sodium hydroxide solution to lead the Ag to be2O attachment to Ba1-xSrxTiO3Nanotube to obtain Ba1-xSrxTiO3/Ag2O composite heterostructure suspension;
d. the Ba obtained in the step c is1-xSrxTiO3/Ag2O composite catalystIrradiating the suspension under ultraviolet lamp for a period of time to obtain Ba1-xSrxTiO3/Ag/Ag2Removing supernatant from suspension O, washing the precipitate with deionized water and ethanol for 3 times, centrifuging, and drying in oven at 60 deg.C for 24 hr to obtain Ba1-xSrxTiO3/Ag/Ag2An O-heterostructure composite catalyst.
2. The method of claim 1, wherein the solvent used in step a is deionized water and the volume of the solvent added is 10mL-30 mL.
3. The method for enhancing the photocatalytic performance of the heterostructure composite material with the pyroelectric effect as recited in claim 1, wherein the muffle furnace calcination temperature in step a is 300 ℃ to 800 ℃.
4. The method of claim 1, wherein the solvent used in the step b of preparing the precursor solution by electrospinning comprises polyvinylpyrrolidone (PVP) and Dimethylformamide (DMF).
5. The method for enhancing the photocatalytic performance of the heterostructure composite material with the pyroelectric effect as recited in claim 1, wherein the calcination temperature in step b is 500 ℃ to 800 ℃.
6. The method for enhancing the photocatalytic performance of heterostructure composite material with pyroelectric effect as claimed in claim 1, wherein AgNO in step c3The concentration of (B) is 0.1mol/L to 1 mol/L.
7. The method of claim 1, wherein the pH value of the adjustment in step c is in the range of 11-13.
8. The method for enhancing the photocatalytic performance of heterostructure composite material with pyroelectric effect according to claim 1, wherein the irradiation time of the ultraviolet lamp in step d is 10min to 60min, the irradiation distance is 5cm to 10cm, preferably, Ba in step d1-xSrxTiO3/Ag/Ag2O heterostructure composite catalyst of Ba1-xSrxTiO3Has pyroelectric effect and can enhance photocatalytic performance, preferably, Ba in step d1-xSrxTiO3/Ag/Ag2O constitutes an S-type or Z-type heterostructure.
9. A pyroelectric effect enhanced heterostructure composite photocatalyst prepared by the method of any one of claims 1 to 8.
10. The use of the pyroelectric effect enhanced heterostructure composite photocatalyst of claim 9 for sterilization, polysaccharide degradation, organic pollutant degradation, and heavy metal ion reduction.
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