CN112209431A - Functionalized BaTiO3Preparation method and application of nano material - Google Patents
Functionalized BaTiO3Preparation method and application of nano material Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 5
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 238000006731 degradation reaction Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000015556 catabolic process Effects 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 238000004729 solvothermal method Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000011858 nanopowder Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000012744 reinforcing agent Substances 0.000 claims description 7
- 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 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims 1
- 229910001626 barium chloride Inorganic materials 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000003623 enhancer Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 56
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 20
- 229940043267 rhodamine b Drugs 0.000 description 20
- 239000000463 material Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002651 drug therapy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a functionalized BaTiO3The preparation method of the nano material comprises the following steps: firstly, dissolving a proper amount of function enhancer in a certain amount of titanium source-ethanol solution, then dropwise adding a proper amount of potassium hydroxide ethanol-deionized water solution, then adding a barium source solution, stirring and mixing to prepare a precursor; transferring the precursor into a reaction kettle for solvothermal reaction; after the reaction is finished, washing and drying are carried out to obtain the functionalized BaTiO3And (3) nano powder. The functionalized BaTiO provided by the invention3The preparation method of the nano material can regulate and control BaTiO by controlling KOH concentration, ethanol-deionized water ratio and solvothermal reaction temperature and time3The crystal grain shape, the size and the surface functional group of the nano powder body to prepare the functionalized BaTiO3The nano material has strong selective adsorption and has potential application in the aspect of piezoelectric catalysis of organic pollutant degradation.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano catalytic materials, and particularly relates to functionalized BaTiO3A preparation method and application of the nano material.
Background
Environmental pollution is a big problem in countries in the world, many toxic and harmful organic pollutants have carcinogenicity, teratogenicity and mutagenicity, the organic pollutants are difficult to remove by adopting the traditional biological treatment process, and the advanced oxidation technology shows unique advantages for the treatment of many toxic and harmful organic pollutants.
Various mechanical energy such as tidal energy, vibration energy and the like widely exist in nature, and are one of clean energy sources. By utilizing the piezoelectric effect of the piezoelectric material, positive and negative polarization charges can be induced on two opposite surfaces of the piezoelectric material through mechanical vibration, and the separation and transfer of free electron-hole pairs are further driven by piezoelectric potentials caused by the positive and negative polarization charges so as to be further connected with O in water2OH formation·O2-、·And (5) OH. The active free radicals can oxidize and decompose organic pollutants difficult to degrade into H2O、CO2And inorganic salt and the like, so that the organic matters are partially or completely mineralized, and the requirement of harmless treatment of pollutants is met. In recent years, people have made a lot of researches on the aspect of piezoelectric catalytic degradation of organic pollutants, and mainly focus on shape control and doping modification of piezoelectric materials to enhance the piezoelectric potential and reduce the band gap, so that the piezoelectric catalytic activity is improved. However, functionalization of piezoelectric materials has not received attention.
Thus, how to provide a functionalized BaTiO3The preparation method and application of the nano material are problems which need to be solved by the technical personnel in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention providesAims to provide a functionalized BaTiO3A preparation method and application of the nano material. The functionalized BaTiO3The preparation method of the nano material can regulate and control BaTiO by controlling KOH concentration, ethanol-deionized water ratio and solvothermal reaction temperature and time3The crystal grain shape, the size and the surface functional group of the nano powder. The preparation method is simple, the reaction conditions are easy to control, and the prepared functionalized BaTiO3The nano material has strong selective adsorption, is applied to the piezoelectric catalysis of the degradation of organic pollutants, improves the piezoelectric catalysis efficiency of the piezoelectric material, improves the catalytic oxidation selectivity, and has good market application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
functionalized BaTiO3The preparation method of the nano material comprises the following steps:
s1, dissolving the functional reinforcing agent in ethanol, and stirring to prepare a solution A; dissolving a titanium source in ethanol, stirring and preparing into a solution B;
s2, adding the solution B into the solution A, stirring and mixing to prepare a solution C; dropwise adding the potassium hydroxide-ethanol-deionized water solution into the solution C, stirring and preparing into a solution D; adding a barium source into the solution D, and stirring to obtain a precursor solution;
s3, transferring the precursor to a reaction kettle for solvothermal reaction; after the reaction is finished, washing and drying are carried out to obtain the functionalized BaTiO3And (3) nano powder.
The technical effect of adopting the scheme is as follows: the preparation method is simple, the reaction conditions are easy to control, and the prepared functional BT nano material has strong selective adsorption.
Preferably, the functional enhancer is polyethylene glycol.
The technical effect of adopting the scheme is as follows: the functional reinforcing agent adopted by the invention can be used in BaTiO3The surface forms oxalic acid functional groups.
Preferably, the dosage ratio of the function enhancer, the titanium source, the potassium hydroxide-ethanol-deionized water solution and the barium source is (0.1-5) g: (0.1-5) mmol: (5-20) mL: (0.1-5) mmol.
The technical effect of adopting the scheme is as follows: the invention adopts the proportion of the functional reinforcing agent, the titanium source, the potassium hydroxide-ethanol-deionized water solution and the barium source to control BaTiO3Crystal phase and morphology of the crystal.
Preferably, the concentration of the potassium hydroxide in the potassium hydroxide-ethanol-deionized water solution is 0.5-5M.
The technical effect of adopting the scheme is as follows: the invention adopts the concentration of the potassium hydroxide to control BaTiO3Crystal size and dispersibility.
Preferably, the total water content in the precursor solution is 5%.
The technical effect of adopting the scheme is as follows: when the water content of the potassium hydroxide-ethanol-deionized water solution is 5 percent, the oxalic acid functionalized BaTiO is formed3The nano material shows strong selective absorption and higher degradation efficiency.
Preferably, the temperature of the solvothermal reaction is 170-240 ℃ and the time is 3-36 h. Further, the temperature of the solvothermal reaction is 190 ℃ and the time is 24 h.
The technical effect of adopting the scheme is as follows: in the present invention, increasing the reaction temperature increases both the equiaxed and banded grain sizes, while extending the reaction time increases the equiaxed grain size and content significantly. However, too high or too low a reaction temperature, and prolonged or shortened reaction time all deteriorate the catalytic activity of the material.
Preferably, the rotation speed of all the stirring in the preparation method is 300-700 r/min, and the time is 10-60 min.
Preferably, the titanium source is tetrabutyl titanate, and the barium source is Ba (OH)2·8H2O。
The invention also provides the functionalized BaTiO3Functionalized BaTiO prepared by preparation method of nano material3Nanomaterial, and functionalized BaTiO3The application of the nano material in the aspect of piezoelectric catalysis of organic pollutant degradation.
The technical effect of adopting the technical scheme is as follows: said functionChemical BT (BaTiO)3) The nano material has strong selective adsorption, the degradation rate of the rhodamine B in the 30min piezoelectric catalysis reaches 91%, and the material has good circulation stability and is a high-efficiency piezoelectric catalysis material.
Through the technical scheme, compared with the prior art, the invention discloses the functionalized BaTiO3The preparation method and the application of the nano material have the following technical effects:
(1) the functionalized BaTiO3The preparation method of the nano material can regulate and control BaTiO by controlling KOH concentration, ethanol-deionized water ratio and solvothermal reaction temperature and time3The crystal grain shape, the size and the surface functional group of the nano powder. The preparation method is simple, the reaction conditions are easy to control, and the prepared functionalized BaTiO3The nano material has strong selective adsorption.
(2) The functionalized BaTiO3The nano material has potential application in the aspects of piezoelectric catalysis of organic pollutant degradation, drug therapy and selective organic synthesis, improves the piezoelectric catalysis efficiency of the piezoelectric material and improves the catalytic oxidation selectivity in the application of piezoelectric catalysis of organic pollutant degradation, has the degradation rate of the piezoelectric catalysis rhodamine B reaching 91% in 30min, has good circulation stability, and is a high-efficiency piezoelectric catalysis material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a drawing of a functionalized BaTiO obtained in example 1 of the present invention3Electron micrographs of nanomaterials, wherein (a) is a scanning electron micrograph of a BT-0-190-24 sample, (b) is a scanning electron micrograph of a BT-5-190-24 sample, (c) is a scanning electron micrograph of a BT-10-190-24 sample, and (d) is a scanning electron micrograph of a BT-0-190-24 sampleA transmission electron micrograph, (e) is a transmission electron micrograph of a BT-5-190-24 sample, and (f) is a high-resolution transmission electron micrograph of the BT-5-190-24 sample and a selected electron diffraction pattern, wherein the insets are the length and thickness distribution curves of nanobelts.
FIG. 2 is a drawing of a functionalized BaTiO obtained in example 1 of the present invention3The infrared spectrum and the X-ray electronic energy spectrum of the nano material are shown as (a) the infrared spectrum of a BT-0-190-24 sample, a BT-5-190-24 sample and a BT-10-190-24 sample, and (b) the X-ray photoelectron energy spectrum of C1s and O1s of the BT-0-190-24 sample, the BT-5-190-24 sample and the BT-10-190-24 sample.
FIG. 3 is a drawing of a functionalized BaTiO obtained in example 1 of the present invention3An application result statistical graph of the nano material, wherein (a) is a concentration ratio C/C of a BT-x-190-24 sample for catalyzing and degrading rhodamine B (RhB) solution0A time-dependent change curve diagram, (b) shows the Degradation Efficiency (DE) and the reaction rate constant (k) of a BT-x-190-24 sample for catalyzing and degrading rhodamine B (RhB) solutionobs) The data statistics map of (1).
FIG. 4 is a diagram of a functionalized BaTiO obtained in example 1 of the present invention3BT-5-190-24 in the nanometer material catalyzes and degrades RhB, Methyl Orange (MO) and tetracycline hydrochloride (TCH) concentration ratio C/C0Time profile and reaction rate constant (k)obs) The data statistics map of (1).
FIG. 5 is a diagram of a functionalized BaTiO obtained in example 1 of the present invention3Concentration ratio C/C of BT-5-190-24 sample in nano material for catalyzing and degrading RhB0Curve as a function of cycle number.
FIG. 6 is a drawing of a functionalized BaTiO obtained in example 2 of the present invention3The electron micrographs of the nanomaterials, wherein (a) is the scanning electron micrograph of the BT-5-190-12 sample, (b) is the scanning electron micrograph of the BT-5-190-36 sample, (c) is the scanning electron micrograph of the BT-5-180-24 sample, and (d) is the scanning electron micrograph of the BT-5-200-24 sample, wherein the inset is the length and thickness distribution curve of the nanobelts.
FIG. 7 is a diagram of a functionalized BaTiO obtained in example 1 of the present invention3A statistical graph of the application results of the nano-materials,wherein (a) is the concentration ratio C/C of BT-5-y-24 for catalyzing and degrading RhB solution0The time-dependent change curve diagram, (b) is the reaction rate constant (k) of BT-5-y-24 catalytic degradation RhB solutionobs) The (C) is the concentration ratio C/C of the BT-5-190-z sample for catalyzing and degrading RhB solution0Time-dependent change curve diagram, (d) is reaction rate constant (k) of BT-5-190-z sample catalyzing and degrading RhB solutionobs) The data statistics map of (1).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials involved in the invention are all obtained from commercial sources, for example, ethanol, potassium hydroxide and the like are all reagents which are used by the technicians in the field conventionally, and the brand sources are not required. In the embodiment of the present invention, the raw material sources used are specifically ethanol (99.7%, hangzhou high-crystalline fine chemical corporation), polyethylene glycol (6000, shanghai alading biochemical technology corporation), butyl titanate (98%, shanghai chemical reagent corporation, national drug group), potassium hydroxide (85%, hangzhou high-crystalline fine chemical corporation), and barium hydroxide (98%, shanghai alading biochemical technology corporation). In the embodiment of the invention, a specific labeling principle is adopted for the sample, and the specific labeling principle is as follows: the sample number is BT-x-y-z, wherein x is the total water content in the precursor solution and is 5%, y is the solvothermal reaction temperature, and z is the solvothermal reaction time.
The embodiment of the invention provides functionalized BaTiO3The preparation method of the nano material comprises the following steps:
s1, dissolving the functional reinforcing agent in ethanol, and stirring to prepare a solution A; dissolving a titanium source in ethanol, stirring and preparing into a solution B;
s2, adding the solution B into the solution A, stirring and mixing to prepare a solution C; dropwise adding the potassium hydroxide-ethanol-deionized water solution into the solution C, stirring and preparing into a solution D; adding a barium source into the solution D, and stirring to obtain a precursor solution;
s3, transferring the precursor to a reaction kettle for solvothermal reaction; after the reaction is finished, washing and drying are carried out to obtain the functionalized BaTiO3And (3) nano powder.
In order to further optimize the technical scheme, the functional enhancer is polyethylene glycol.
In order to further optimize the technical scheme, the dosage ratio of the functional enhancer, the titanium source, the potassium hydroxide-ethanol-deionized water solution and the barium source is (0.1-5) g: (0.1-5) mmol: (5-20) mL: (0.1-5) mmol.
In order to further optimize the above technical solution, the total water content in the precursor solution is 5%.
In order to further optimize the technical scheme, the temperature of the solvothermal reaction is 170-240 ℃, and the time is 3-36 h.
In order to further optimize the technical scheme, the titanium source is tetrabutyl titanate.
In order to further optimize the technical scheme, the barium source is Ba (OH)2·8H2O。
The invention also provides the functionalized BaTiO3Functionalized BaTiO prepared by preparation method of nano material3Nanomaterial, and functionalized BaTiO3The application of the nano material in the aspect of piezoelectric catalysis of organic pollutant degradation.
In order to further optimize the technical scheme, the method is applied to piezoelectric catalysis of organic pollutants in the dye liquor sewage.
Example 1
Dissolving 1g of polyethylene glycol in 12ml of ethanol solution, and stirring for 10-60 min; simultaneously dissolving 1mmol of butyl titanate in 10ml of ethanol solution, stirring for 10-60min, and adding the solution into polyethylene glycol solution; dripping 12ml of 2M potassium hydroxide-ethanol-deionized water solution with different water contents into the mixed solution, stirring for 10-60min, and adding 1mmol of Ba (OH)2·8H2O, preparing a precursor; finally, the precursor is moved into a 100ml reaction kettle with a tetrafluoroethylene lining, and the solvent thermal reaction is carried out for 24 hours at 190 ℃; and after the reaction is finished, washing and drying to obtain the functional BT nano powder.
Wherein the water content in the precursor is respectively 0, 5%, 10%, 15%, 20% and 30%, other preparation parameters and raw material dosage are not changed, and correspondingly, the obtained functionalized BT nano-powder samples are respectively BT-0-190-24, BT-5-190-24, BT-10-190-24, BT-15-190-24, BT-20-190-24 and BT-30-190-24.
Fig. 1 shows scanning electron micrographs and projection electron micrographs of BT-0-190-24, BT-5-190-24, BT-10-190-24 samples, and it was found that the microstructure of the samples consisted of equiaxed grains and banded grains, with equiaxed grain size increasing with increasing moisture content and banded grain size decreasing in length and thickness. The prepared BT sample can be determined to be polycrystalline barium titanate with a perovskite structure from the high-resolution transmission electron micrograph and the corresponding selected electron diffraction pattern. Based on the infrared spectrum of BT-0-190-24, BT-5-190-24 and BT-10-190-24 and the X-ray photoelectron spectrum of C1s and O1s given in FIG. 2, the oxalic acid can be determined to be adsorbed on the surface of BT-5-190-24, and the acetic acid can be determined to be adsorbed on the surfaces of BT-0-190-24 and BT-10-190-24.
The functional BT nanopowder obtained in this example was subjected to a degradation test.
Respectively putting 0.1g of BT nano powder into 100ml of RhB, MO and TCH solutions with the concentration of 5mg/L, stirring for 60min in a dark environment, placing the solutions into an ultrasonic water bath with the frequency of 40kHz and the power of 100W for catalytic degradation after adsorption-desorption balance, and taking the solutions once every several minutes to measure the ultraviolet-visible absorption spectra.
FIG. 3 shows the concentration ratio C/C of the catalytic degradation RhB solution of the BT-x-190-24 sample0The result shows that the BT-5-190-24 sample has high degradation efficiency, namely after 30min of piezoelectric catalytic reaction, the catalytic degradation efficiency is 91 percent, and the reaction rate constant is 0.068min-1. Further, FIG. 4 shows the concentration ratio C/C of the BT-5-190-24 sample for catalyzing the degradation of RhB, Methyl Orange (MO) and tetracycline hydrochloride (TCH)0Time-dependent curve and reaction rate constant (k)obs) The BT-5-190-24 sample adsorbs RhB, MO and TCH pollutants, and is found to have strong adsorption effect on RhB, so that high degradation efficiency is caused. FIG. 5 shows the concentration ratio C/C of catalytic degradation RhB of the BT-5-190-24 sample0The cycle stability was found to be good as a function of the cycle number.
Example 2
Dissolving 1g of polyethylene glycol in 12ml of ethanol solution, and stirring for 10-60 min; simultaneously dissolving 1mmol of butyl titanate in 10ml of ethanol solution, stirring for 10-60min, and adding the solution into polyethylene glycol solution; dripping 12ml of 2M potassium hydroxide-ethanol-deionized water solution with the water content of 5% into the mixed solution, stirring for 10-60min, and adding 1mmol of Ba (OH)2·8H2O, preparing a precursor; finally, the precursor is moved into a 100ml reaction kettle with a tetrafluoroethylene lining, and the solvent thermal reaction is carried out for 6 to 36 hours at the temperature of 170-; and after the reaction is finished, washing and drying to obtain the functional BT nano powder.
Wherein the temperature of the solvothermal reaction is respectively set to 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, the reaction time is 24 hours, other preparation parameters and the raw material dosage are not changed, and correspondingly, the obtained functionalized BT nano-powder samples are respectively BT-5-170-24, BT-5-180-24, BT-5-190-24, BT-5-200-24 and BT-5-210-24.
The solvothermal reaction time is respectively set to 6h, 12h, 24h and 36h, the reaction temperature is 190 ℃, other preparation parameters and the raw material dosage are unchanged, and correspondingly, the obtained functionalized BT nano-powder samples are BT-5-190-6, BT-5-190-12, BT-5-190-24 and BT-5-190-36.
Fig. 6 shows scanning electron micrographs of BT samples produced at different solvothermal reaction temperatures and times, and it was found that increasing the reaction temperature increased both the equiaxed and banded grain sizes, while extending the reaction time the equiaxed grain size and content increased significantly.
The functional BT nanopowder obtained in this example was subjected to a degradation test.
Respectively putting 0.1g of BT nano powder into 100ml of RhB solution with the concentration of 5mg/L, stirring for 60min in a dark environment, placing the solution into an ultrasonic water bath with the frequency of 40kHz and the power of 100W for catalytic degradation after adsorption-desorption balance, and taking the solution every several minutes to measure the ultraviolet-visible absorption spectrum of the solution.
FIG. 7 shows the concentration ratio C/C of BT-like catalytically degraded RhB solutions prepared at different solvothermal reaction temperatures and times0Degradation efficiency and reaction rate constant, and consequently, it has been found that too high or too low a reaction temperature, extension or shortening of the reaction time worsens the catalytic activity of the material.
In conclusion, the functionalized BaTiO3The preparation method of the nano material can regulate and control BaTiO by controlling KOH concentration, ethanol-deionized water ratio and solvothermal reaction temperature and time3The crystal grain shape, the size and the surface functional group of the nano powder. The preparation method is simple, the reaction conditions are easy to control, and the prepared functionalized BaTiO3The nano material has strong selective adsorption. The functionalized BaTiO3The nanometer material is applied to the piezoelectric catalysis of the degradation of organic pollutants, the piezoelectric catalysis efficiency of the piezoelectric material is improved, the catalytic oxidation selectivity is improved, the degradation rate of the rhodamine B in the 30min piezoelectric catalysis reaches 91%, the cycle stability is good, and the nanometer material is an efficient piezoelectric catalysis material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. Functionalized BaTiO3The preparation method of the nano material is characterized by comprising the following steps:
s1, dissolving the functional reinforcing agent in ethanol, and stirring to prepare a solution A; dissolving a titanium source in ethanol, and stirring to prepare a solution B;
s2, adding the solution B into the solution A, stirring and mixing to prepare a solution C;
dropwise adding the potassium hydroxide-ethanol-deionized water solution into the solution C, and stirring to prepare a solution D; adding a barium source into the solution D, and stirring to obtain a precursor solution;
s3, transferring the precursor to a reaction kettle for solvothermal reaction; after the reaction is finished, washing and drying are carried out to obtain the functionalized BaTiO3And (3) nano powder.
2. A functionalized BaTiO according to claim 13The preparation method of the nano material is characterized in that the functional reinforcing agent is polyethylene glycol.
3. A functionalized BaTiO according to claim 13The preparation method of the nano material is characterized in that the dosage ratio of the functional reinforcing agent to the titanium source to the potassium hydroxide-ethanol-deionized water solution to the barium source is (0.1-5) g: (0.1-5) mmol: (5-20) mL: (0.1-5) mmol.
4. A functionalized BaTiO according to claim 33The preparation method of the nano material is characterized in that the concentration of potassium hydroxide in the potassium hydroxide-ethanol-deionized water solution is 0.5-5M.
5. A functionalized BaTiO according to claim 43The preparation method of the nano material is characterized in that the total water content in the precursor solution is 5%.
6. A functionalized BaTiO according to claim 13The preparation method of the nano material is characterized in that the temperature of the solvothermal reaction is 170-240 ℃ and the time is 3-36 h.
7. A functionalized BaTiO according to claim 13A method for preparing a nanomaterial, characterized in that the titanium isThe source is tetrabutyl titanate or titanium tetrachloride, and the barium source is Ba (OH)2·8H2O or barium chloride or barium nitrate.
8. Functionalized BaTiO3Nanomaterial characterized by the functionalized BaTiO according to any of claims 1 to 73The preparation method of the nano material.
9. Functionalized BaTiO3Use of nanomaterials, characterised in that the functionalised BaTiO according to claim 83The application of the nano material in the aspect of piezoelectric catalysis of organic pollutant degradation.
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