CN111996618B - Vanadium-doped strontium titanate nanofiber and preparation method and application thereof - Google Patents
Vanadium-doped strontium titanate nanofiber and preparation method and application thereof Download PDFInfo
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002121 nanofiber Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 150000003681 vanadium Chemical class 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 18
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical group [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 23
- 229910002367 SrTiO Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 229910052720 vanadium Inorganic materials 0.000 description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 14
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001523 electrospinning Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910002370 SrTiO3 Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001456 vanadium ion Inorganic materials 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 229910020215 Pb(Mg1/3Nb2/3)O3PbTiO3 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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Abstract
The invention discloses a vanadium-doped strontium titanate nanofiber, which comprises the following steps: carrying out electrostatic spinning on the vanadium-doped strontium titanate electrostatic spinning precursor solution to obtain a fiber membrane; calcining the fiber membrane to obtain vanadium-doped strontium titanate nanofibers; the vanadium-doped strontium titanate electrostatic spinning precursor solution comprises vanadium salt, strontium salt, titanium salt, high polymer and solvent. The vanadium-doped strontium titanate nanofiber piezoelectric material has a non-centrosymmetric structure in the construction of a piezoelectric catalytic nanomaterial, is an excellent ferroelectric material, has an internal space charge layer, can effectively generate piezoelectric induced charges, has good piezoelectric performance, and can efficiently degrade and remove organic pollutants in a water body under the action of external ultrasonic vibration.
Description
Technical Field
The invention relates to the technical field of nano piezoelectric materials and piezoelectric catalysis, in particular to a preparation method of a vanadium-doped strontium titanate nanofiber piezoelectric material and application of the vanadium-doped strontium titanate nanofiber piezoelectric material in removing organic pollutants in a water body through piezoelectric catalysis.
Background
In recent years, the piezoelectric effect caused by piezoelectric polarization of piezoelectric materials has been widely applied to sensors, nanogenerators, and piezoelectric field effect transistors. In addition, nanostructured piezoelectric materials are useful for photocatalytic environmental remediation and waterThe application in the decomposition aspect also draws wide attention, and particularly shows that the piezoelectric effect can enhance the separation of photon-generated carriers, so that the photocatalytic activity of the piezoelectric semiconductor catalyst is improved. Recently, researchers have discovered a new piezoelectric phenomenon, called "piezo-catalysis". This phenomenon indicates that even in the absence of optical excitation, the piezoelectric potential caused by mechanical agitation can initiate various catalytic reactions, such as water decomposition, degradation of organic pollutants, and even promote the synthesis of organic compounds. At present, the materials exhibiting piezoelectric catalytic activity are mainly ferroelectric crystals with spontaneous polarization, including BaTiO3、BiFeO3、Pb(Zr0.52Ti0.48)O3、Pb(Mg1/3Nb2/3)O3-PbTiO3、MoS2And MoSe2. Studies have shown that barium titanate and lead zirconate titanate are strong ferroelectrics with high piezoelectric coefficients and dielectric constants, however these ferroelectrics are highly insulating and have poor electrical conductivity; one solution to ameliorate this disadvantage is to replace the insulating ferroelectrics with semiconductor materials with similar permanent polarization. Strontium titanate (SrTiO)3) Is an ABO3Perovskite type, which is also a nascent ferroelectric, has many transition metal elements doped into the crystal lattice of strontium titanate, such as La, Nb, Ta, Cr, Ir, Mn, Rh, etc., due to the size difference between the impurity and the replaced atom, the crystal lattice distortion is caused, so that the symmetry of the structure is reduced, thereby having great influence on the electrical property, magnetic property and dielectric property of perovskite, and the research on piezoelectric catalysis is still in an early stage, and more new strategies are urgently needed to be developed to enhance the catalytic activity.
Disclosure of Invention
The invention aims to provide a vanadium-doped strontium titanate nanofiber piezoelectric material and a preparation method thereof, and the constructed piezoelectric material can effectively degrade and remove organic pollutants in a water body under pure ultrasonic vibration.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
vanadium doped strontium titanate nanofibers (V-SrTiO)3NFs) and the preparation method comprises the following steps: carrying out electrostatic spinning on the vanadium-doped strontium titanate electrostatic spinning precursor solution to obtain a fiber membrane; calcining the fiber membrane to obtain vanadium-doped strontium titanate nanofibers; the vanadium-doped strontium titanate electrostatic spinning precursor solution comprises vanadium salt, strontium salt, titanium salt, high polymer and solvent.
A method for degrading organic pollutants in water, comprising the steps of: carrying out electrostatic spinning on the vanadium-doped strontium titanate electrostatic spinning precursor solution to obtain a fiber membrane; calcining the fiber membrane to obtain vanadium-doped strontium titanate nanofibers; adding vanadium-doped strontium titanate nanofibers into water containing organic pollutants, and then carrying out ultrasonic treatment to remove the organic pollutants in the water; the vanadium-doped strontium titanate electrostatic spinning precursor solution comprises vanadium salt, strontium salt, titanium salt and high polymer.
In the invention, vanadium salt is taken as a vanadium source, and the vanadium source is added into a mixed solution containing strontium salt, titanium salt and high polymer to prepare a vanadium-doped strontium titanate electrostatic spinning precursor solution; injecting the obtained vanadium-doped strontium titanate electrostatic spinning precursor solution into an injector, and performing electrostatic spinning to obtain a polymer fiber membrane; and then calcining the polymer fiber in the air atmosphere to obtain the one-dimensional vanadium-doped strontium titanate nanofiber material which can be used for degrading organic pollutants in water, for example, adding the vanadium-doped strontium titanate nanofiber into water containing pollutants, stirring, and then carrying out ultrasonic treatment to complete removal of the organic pollutants in the water body.
In the invention, strontium salt is strontium nitrate, titanium salt is tetrabutyl titanate or tetraisopropyl titanate, vanadium salt is vanadyl acetylacetonate, a solvent is ethanol, N-dimethylformamide, acetic acid and water, and a polymer is polyvinylpyrrolidone; furthermore, the volume ratio of the ethanol to the N, N-dimethylformamide to the acetic acid to the water is (1-1.5) to 1. And further, sequentially adding the four solvents and titanium salt into a glass bottle containing strontium salt and vanadium salt to obtain a mixed solution, stirring at room temperature until the mixed solution is clear, adding a polymer into the mixed solution, and stirring to obtain a transparent pale yellow solution which is a vanadium-doped strontium titanate electrostatic spinning precursor solution. Preferably, the molar amount of the vanadium salt is 0 to 1% of the molar amount of the strontium nitrate.
In the invention, the obtained vanadium-doped strontium titanate electrostatic spinning precursor solution is injected into an injector, and then the vertical distance between the tip of a nozzle and a grounded stainless steel receiver and electrostatic spinning voltage are set through electrostatic spinning equipment to carry out spinning; preferably, the vertical distance is 14-16 cm; the voltage is 15-20 kV.
In the invention, the calcining temperature is 550-650oC, the temperature rise rate is 1-2oC/min for 3-5 hours.
In the invention, the organic pollutant is bisphenol A, and ultrasonic treatment is carried out by stirring; the stirring is preferably carried out for 1 hour in a dark place, and then pure ultrasonic treatment is carried out, wherein the power of the ultrasonic treatment is preferably 100-150W.
The invention discloses an application of the vanadium-doped strontium titanate nanofiber material in removing water pollutants; the preferred organic contaminant is bisphenol a.
In the construction of the catalytic nanomaterial, the vanadium-doped strontium titanate nanofiber material has a non-centrosymmetric structure and an internal space charge layer, and can effectively generate piezoelectric induced charges, so that inherent free charges (electrons and holes) can be effectively separated under mechanical vibration and participate in a piezoelectric catalytic process; in addition, the one-dimensional piezoelectric nanofiber is easy to deform due to flexibility, and the piezoelectric potential of the one-dimensional piezoelectric nanofiber is usually greater than that of the nano particles, so that the one-dimensional piezoelectric nanofiber has stronger piezoelectric catalytic activity; furthermore, it is a doped ABO3The perovskite material can still keep the structural stability after being doped, and leads to the reduction of the distortion and symmetry of the structure, thereby improving the piezoelectric property of the material and leading the perovskite structure material to have important application in dielectric ceramics.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the vanadium-doped strontium titanate nanofiber piezoelectric material disclosed by the invention is simple in preparation method and uniform in appearance, and the easy-deformation property of the vanadium-doped strontium titanate nanofiber piezoelectric material can further improve the piezoelectric catalytic performance;
2. the vanadium-doped strontium titanate nanofiber piezoelectric material disclosed by the invention avoids redundant charges generated in a doped sample, improves the piezoelectric performance of the material, and the reduction of the band gap of strontium titanate caused by vanadium doping can enable more free carriers in the piezoelectric material to participate in the redox process;
3. the vanadium-doped strontium titanate nanofiber piezoelectric material disclosed by the invention has higher piezoelectric coefficient and dielectric constant, so that the material has better piezoelectric performance, and can efficiently degrade and remove organic pollutants in a water body under the action of external ultrasonic vibration.
Drawings
FIG. 1 shows vanadium-doped strontium titanate nanofibers (V-SrTiO)3NFs) scanning electron micrographs;
FIG. 2 is a transmission electron micrograph of vanadium doped strontium titanate nanofibers;
FIG. 3 is an XRD pattern of vanadium doped strontium titanate nanofibers;
FIG. 4 is a graph of the UV-VIS absorption spectrum of vanadium-doped strontium titanate nanofibers;
FIG. 5 is a graph showing the effect of degrading bisphenol A by vanadium-doped strontium titanate nanofibers.
Detailed Description
The vanadium-doped strontium titanate nanofiber disclosed by the invention shows a quite large polarization effect when lattice distortion is caused by interface stress, so that piezoelectric induction charges can be effectively generated, and in addition, compared with barium titanate, the vanadium-doped strontium titanate nanofiber has higher room-temperature electron mobility (approximately equal to 5-8 cm)2 V−1 s−1) Due to the easy deformation property, the piezoelectric potential of one-dimensional or two-dimensional piezoelectric materials is larger than that of particles, and one-dimensional piezoelectric nanomaterials, such as nanofibers and nanowires, have the advantages of large specific surface area, light weight, small size, high aspect ratio and the like, and the larger bending flexibility of the materials leads to more sensitive response of the materials to external stress, so that the materials can effectively separate free charge carriers even under the minimum strain.
Example one
Vanadium doped strontium titanate nanofiber piezoelectric material (0.25 mol% V-SrTiO)3NFs) preparation: firstly, 1 mmol of strontium nitrate and 0.0025mmol of acetylacetoneDissolving vanadyl into a solution containing 1.5 mL of ethanol, 1.5 mL of N, N-dimethylformamide, 1.5 mL of acetic acid, 1.5 mL of deionized water and tetrabutyl titanate, stirring until the solution is clear, adding 0.5 g of polyvinylpyrrolidone into the solution, stirring at room temperature for 12 hours, injecting the obtained transparent pale yellow solution into a syringe for electrostatic spinning, wherein the vertical distance between the nozzle tip of an electrospinning device and a grounded stainless steel receiver and the electrostatic spinning voltage are respectively 15 cm and 15 kV; after the electrostatic spinning was completed, the obtained product was exposed to air atmosphere at 2 deg.foThe temperature rising rate of C/min is increased from room temperature to 550oAnd C, calcining for 3 hours again to obtain the vanadium-doped strontium titanate nanofiber piezoelectric material (0.25 mol percent V-SrTiO)3NFs), wherein the mol ratio of the strontium nitrate, the tetrabutyl titanate and the vanadyl acetylacetonate is 1:0.9975: 0.0025.
Example two
Vanadium doped strontium titanate nanofiber piezoelectric material (0.5 mol% V-SrTiO)3NFs) preparation: firstly, dissolving 1 mmol of strontium nitrate and 0.005 mmol of vanadyl acetylacetonate in a solution containing 1.5 mL of ethanol, 1.5 mL of N, N-dimethylformamide, 1.5 mL of acetic acid, 1.5 mL of deionized water and tetrabutyl titanate, stirring until the solution is clear, adding 0.5 g of polyvinylpyrrolidone into the solution, stirring at room temperature for 12 hours, injecting the obtained transparent pale yellow solution into a syringe for electrostatic spinning, wherein the vertical distance between the nozzle tip of an electrospinning device and a grounded stainless steel receiver and the electrostatic spinning voltage are respectively 15 cm and 15 kV; after the electrostatic spinning was completed, the obtained product was exposed to air atmosphere at 2 deg.foThe temperature rising rate of C/min is increased from room temperature to 550oAnd C, calcining for 3 hours again to obtain the vanadium-doped strontium titanate nanofiber piezoelectric material (0.5 mol percent V-SrTiO)3NFs), wherein the mol ratio of the strontium nitrate, the tetrabutyl titanate and the vanadyl acetylacetonate is 1:0.995: 0.005. As can be seen from fig. 1 and 2, the 0.5mol% vanadium-doped strontium titanate nanofibers are mainly formed by interlacing uniform, straight and elongated nanostructures. Meanwhile, no diffraction peak of other impurities exists in the XRD pattern (figure 3) of the vanadium-doped strontium titanate nano-fiber, and the existence of diffraction peaks of other impurities is still ensuredThe diffraction peaks of the standard perovskite strontium titanate are maintained, which indicates that vanadium has successfully replaced titanium ions into the strontium titanate lattice.
EXAMPLE III
Vanadium doped strontium titanate nanofiber piezoelectric material (1.0 mol% V-SrTiO)3NFs) preparation: 1 mmol strontium nitrate and 0.01 mmol vanadyl acetylacetonate were first dissolved in a solution comprising 1.5 mL ethanol, 1.5 mL N, N-dimethylformamide, 1.5 mL acetic acid, 1.5 mL deionized water and tetrabutyl titanate. After stirring to be clear, 0.5 g of polyvinylpyrrolidone was further added thereto, and after stirring at room temperature for 12 hours, the obtained transparent pale yellow solution was injected into a syringe. The vertical distance between the nozzle tip of the electrospinning apparatus and the grounded stainless steel receiver and the electrospinning voltage were 15 cm and 15 kV, respectively. After the electrostatic spinning was completed, the obtained product was exposed to air atmosphere at 2 deg.foThe temperature rising rate of C/min is increased from room temperature to 550oAnd C, calcining for 3 hours again to obtain the vanadium-doped strontium titanate nanofiber piezoelectric material (1.0 mol percent V-SrTiO)3NFs). Wherein the mol ratio of strontium nitrate, tetrabutyl titanate and vanadyl acetylacetonate is 1:0.99: 0.01.
Comparative example
Strontium titanate nanofiber piezoelectric material (SrTiO)3NFs) preparation: firstly, 1 mmol of Sr (NO)3)2Dissolve into a solution containing 1.5 mL ethanol, 1.5 mL N, N-dimethylformamide, 1.5 mL acetic acid, 1.5 mL deionized water, and 0.34 mL tetrabutyltitanate. After stirring to be clear, 0.5 g of polyvinylpyrrolidone was further added thereto, and after stirring at room temperature for 12 hours, the obtained transparent pale yellow solution was injected into a syringe. The vertical distance between the nozzle tip of the electrospinning apparatus and the grounded stainless steel receiver and the electrospinning voltage were 15 cm and 15 kV, respectively. After the electrostatic spinning was completed, the obtained product was exposed to air atmosphere at 2 deg.foThe temperature rising rate of C/min is increased from room temperature to 550oAnd C, calcining for 3 hours to obtain the strontium titanate nanofiber piezoelectric material (SrTiO)3 NFs）。
FIG. 4 is a vanadium doped strontium titanate nanofiber (V-SrTiO)3NFs), strontium titanate nanofiber piezoelectric material (SrTiO)3NFs) in the sample. From fig. 4 it can be seen that the absorption band edge of the vanadium doped strontium titanate nanofibers is significantly red shifted into the visible region, indicating that vanadium ions have been doped into the crystal lattice of strontium titanate.
Example four
Vanadium doped strontium titanate nanofiber piezoelectric material (0.5 mol% V-SrTiO)3NFs) piezo-electric catalytic degradation experiments on bisphenol A: 6 mg of the piezoelectric catalyst obtained in example two, 0.5mol% V-SrTiO3NFs, in 10 mL of 10 mg/L aqueous bisphenol A solution. Stirring for one hour in dark to reach adsorption-desorption equilibrium. After balancing, the reactor filled with the bisphenol A aqueous solution is placed in an ultrasonic cleaner, the ultrasonic cleaner is opened, the power is adjusted to 150W, 1 mL of sample is taken every 8 minutes, the retention time is recorded by using high performance liquid chromatography, and the liquid phase peak area corresponding to the retention time is recorded, so that the concentration of bisphenol A in the corresponding water sample is obtained. FIG. 5 is a graph showing the residual ratio of bisphenol A with respect to time. As can be seen from FIG. 5, after the addition of 0.5mol% of V-SrTiO3NFs piezoelectric catalyst, and after 24 min under the condition of separately applying ultrasound and completely protecting from light, the bisphenol A in the aqueous solution is completely removed.
The catalyst materials of other examples were tested in the same manner, and the residual ratios of bisphenol A in the aqueous solution after 24 min of light irradiation were 12% in example one, 10% in example three, and 22% in comparative example. The vanadyl acetylacetonate obtained in example II was replaced by ammonium metavanadate in the same manner as in the previous example to obtain 0.5mol% V-SrTiO3NFs, mixing the 0.5mol% V-SrTiO3NFs through the same piezoelectric catalytic degradation experiment of bisphenol A, after 24 min of ultrasonic treatment, 25% of bisphenol A remained in the aqueous solution. The ultrasonic power in example four was adjusted to 60W, and 0.5mol% V-SrTiO was added in the same manner as in the other examples3NFs through the same piezoelectric catalytic degradation experiment of bisphenol A, after 24 min of ultrasonic treatment, 70% of bisphenol A remained in the aqueous solution.
The rhodium trichloride trihydrate in the existing CN110743541A comparative example is replaced by the vanadyl acetylacetonate with equal molar quantity, and the rest is the same as the preparation method of the comparative example, vanadium-doped strontium titanate nano-particles are prepared by a hydrothermal method, and the vanadium doping quantity is also 0.5 mol%. After the same piezoelectric catalytic degradation experiment of bisphenol A, bisphenol A in the aqueous solution remained 37% after the ultrasonic treatment for 24 min.
The solvent in the examples and the comparative examples is replaced by ethanol, N-dimethylformamide and deionized water, and the vanadium-doped strontium titanate nanofiber or strontium titanate nanofiber cannot be obtained successfully by the same method. The invention discloses a preparation method of a vanadium-doped strontium titanate nanofiber material and application of the vanadium-doped strontium titanate nanofiber material in removing organic pollutants (bisphenol A) in a water body through piezoelectric catalysis. The novel inorganic nano piezoelectric material of the vanadium-doped strontium titanate nano fiber is obtained by a simple electrostatic spinning method. The vanadium-doped strontium titanate nanofiber prepared by the method has the advantages of large specific surface area, light weight, small size, high aspect ratio and the like, and the response of the material to external stress is more sensitive due to the easily deformable property of the vanadium-doped strontium titanate nanofiber, so that the piezoelectric potential is enhanced, and the piezoelectric catalytic activity is further enhanced. Meanwhile, the vanadium-doped strontium titanate nanofiber disclosed by the invention is formed by doping vanadium ions into titanium sites, so that the reduction of piezoelectric catalytic performance caused by charge imbalance caused by the existing substitution is avoided; in addition, vanadium-doped strontium titanate causes the symmetry of the perovskite structure to be reduced, thereby further improving the piezoelectric performance of the perovskite structure; in addition, the catalyst has higher piezoelectric coefficient and dielectric constant, so that the vanadium-doped strontium titanate can be used for efficiently catalyzing and degrading organic pollutants in a water body by fully utilizing the doped low band gap even under the condition of single ultrasonic vibration.
Claims (10)
1. The vanadium-doped strontium titanate nanofiber is characterized in that the preparation method of the vanadium-doped strontium titanate nanofiber comprises the following steps: carrying out electrostatic spinning on the vanadium-doped strontium titanate electrostatic spinning precursor solution to obtain a fiber membrane; calcining the fiber membrane to obtain vanadium-doped strontium titanate nanofibers; the vanadium-doped strontium titanate electrostatic spinning precursor solution comprises vanadium salt, strontium salt, titanium salt, high polymer and solvent.
2. The vanadium-doped strontium titanate nanofiber according to claim 1, wherein the strontium salt is strontium nitrate, the titanium salt is tetrabutyl titanate or tetraisopropyl titanate, the vanadium salt is vanadyl acetylacetonate, the solvent is ethanol, N-dimethylformamide, acetic acid and water, and the polymer is polyvinylpyrrolidone.
3. The vanadium-doped strontium titanate nanofiber according to claim 2, wherein the volume ratio of ethanol, N-dimethylformamide, acetic acid and water is (1-1.5) to 1.
4. The vanadium-doped strontium titanate nanofiber according to claim 1, wherein the molar amount of the vanadium salt is 0-1% of the molar amount of the strontium salt.
5. The vanadium-doped strontium titanate nanofiber according to claim 1, wherein the vertical distance during electrostatic spinning is 14-16 cm; the voltage is 15-20 kV.
6. The vanadium-doped strontium titanate nanofiber according to claim 1, wherein the calcination temperature is 550-650 ℃, the temperature rise rate is 1-2 ℃/min, and the time is 3-5 hours.
7. Use of vanadium-doped strontium titanate nanofibers according to claim 1 for the preparation of piezoelectric materials.
8. Use of the vanadium-doped strontium titanate nanofibers according to claim 1 in water treatment.
9. Use according to claim 8, characterized in that the water treatment is carried out under ultrasound.
10. Use according to claim 8, wherein the water treatment is an organic pollutant treatment.
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