CN111604047A - Photocatalyst with ferroelectricity and preparation method thereof - Google Patents
Photocatalyst with ferroelectricity and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 230000005621 ferroelectricity Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 14
- 238000009837 dry grinding Methods 0.000 claims description 12
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- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 6
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- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 9
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- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 14
- 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 12
- 229940043267 rhodamine b Drugs 0.000 description 12
- 239000011858 nanopowder Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
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- 239000004408 titanium dioxide Substances 0.000 description 3
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- 229910002113 barium titanate 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
- 238000005452 bending Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a photocatalyst with ferroelectricity and a preparation method thereof, and the general formula of the structure of the photocatalyst is RbBin‑1BnO3n+1Wherein the metal B is Nb or Nb and Ti, n is more than or equal to 2 and less than or equal to 4, and the metal B is obtained by simple solid phase synthesis and ball millingTo photocatalysts having a particle size on the order of nanometers. The photocatalyst is nano-scale, can shorten the time for a current carrier to migrate to a reaction site, and improves the reaction activity; the material has ferroelectricity, and an internal electric field generated by spontaneous polarization of the material can improve the separation of photo-generated electrons and holes and prevent recombination; the surface of the catalyst can be further coated by a cocatalyst WC through high-energy ball milling, and the photocatalysis efficiency is high.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and relates to a ferroelectric photocatalyst and a preparation method thereof.
Background
Photocatalytic materials have been studied for nearly fifty years, and titanium dioxide (TiO) was discovered and reported by Japanese researchers from the first 19722) Since photocatalytic materials are used for photolyzing water, researchers are constantly working on improving the light conversion efficiency of existing materials and searching for new high-performance materials. The commonly used photocatalysts at present comprise oxides such as titanium dioxide, zinc oxide, tin oxide, zirconium dioxide and the like, and sulfide semiconductors. However, the oxide catalyst material has a large forbidden band width, and the sulfide catalyst has a small forbidden band width but unstable chemical properties, which limits its application in the field of photocatalysis. Therefore, the modification of the photocatalyst and the development of new catalysts have become the hot directions for the research of the photocatalytic technology.
The photocatalysis process mainly comprises the following three steps: absorption of light energy, separation and migration of photo-generated electrons and holes, surface adsorption and reaction. In recent years, ferroelectric materials have attracted much attention as novel photocatalytic materials. On one hand, the ferroelectric material forms an internal electric field due to spontaneous polarization, thereby promoting the separation of electrons and holes in the photocatalytic reaction; on the other hand, a depolarization field inside the ferroelectric material can cause band bending, resulting in a spatially selective reaction. Ferroelectricity has been used to improve the photocatalytic properties of barium titanate (BaTiO)3) Bismuth ferrite (BiFeO)3) Lead zirconate titanate (Pb (Zr)0.3Ti0.7)O3) Etc. were confirmed. The shape of the photocatalytic material is controlled, and the photocatalytic efficiency can be effectively improved by using the cocatalyst. Nano materialThe material has higher specific surface energy, more reaction sites and higher reaction activity; meanwhile, the nano material has small particle size, so that the path for a carrier to migrate to a particle surface is short, the recombination probability is low, and the nano material is favorable for obtaining high photocatalytic performance. On the other hand, the promoters commonly used at present are noble metals such as Pt, Rh and Ru, but these materials are expensive and cannot be widely used.
In summary, the existing photocatalytic materials have the disadvantage of low photocatalytic efficiency due to easy recombination of photo-generated electrons and holes, and therefore, it is very important to develop a catalyst with high catalytic activity and a preparation method thereof.
Disclosure of Invention
Aiming at the defect that the existing photocatalytic material is low in photocatalytic efficiency due to the fact that photo-generated electrons and holes are easy to combine, the invention aims to provide the photocatalyst with ferroelectricity and the preparation method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a ferroelectric photocatalyst with a general structural formula of RbBin-1BnO3n+1Wherein the metal B is Nb or Nb and Ti, and n is more than or equal to 2 and less than or equal to 4.
Preferably, the metal B is Nb and Ti, and the molar ratio of Nb to Ti is 1: 2, n is 3.
Preferably, the surface of the photocatalyst is further coated with WC, and RbBi is obtained by coating RbBin-1BnO3n+1Placing the mixture in a WC tank for high-energy ball milling to obtain the product.
The invention also provides a preparation method of the photocatalyst, which comprises the following steps:
(1) will Rb2CO3、BiO2And an oxide of metal B, wherein Rb is mixed according to a set molar ratio2CO3Excess of1-5 wt%, wet grinding and drying to obtain mixed powder for later use;
(2) carrying out solid-phase synthesis on the mixed powder obtained in the step (1) at high temperature, then carrying out dry grinding, and repeating the solid-phase synthesis for 1-2 times to obtain synthetic powder for later use;
(3) and (3) performing ball milling on the synthetic powder obtained in the step (2) to obtain nanoscale sample powder.
Preferably, in the step (1), the wet milling process parameters are as follows: the ball milling tank is a nylon tank, the ball milling medium is alcohol, the rotating speed is 100-; the drying temperature is 80-100 deg.C, and the drying time is 8-12 h.
In the preferable scheme, in the step (2), the temperature of solid phase synthesis is 850-1000 ℃, and the time is 4-24 h; the dry milling process parameters are as follows: the rotating speed is 50-100rmp, and the ball milling time is 2-6 h.
In the preferable scheme, in the step (3), the ball milling mode is common ball milling, and the technological parameters are as follows: the ball milling tank is a nylon tank, and the grinding ball is ZrO2Ball, the ball milling medium is alcohol, the rotating speed is 300-n-1BnO3n+1；
Or the ball milling mode is high-energy ball milling, and the technological parameters are as follows: the ball milling tank is a WC tank, and the grinding balls are ZrO2The ball milling medium is water, the rotating speed is 800-n-1BnO3n+1. The inventors surprisingly found that by placing the synthetic powder after solid phase synthesis in a WC tank for high-energy ball milling, the surface of the synthetic powder can be wrapped by WC, and the WC can be used as a cocatalyst, so that the composition of photo-generated electrons and holes is effectively prevented, and the photocatalytic performance of the catalyst is greatly improved.
Compared with the prior art, the invention has the advantages that:
(1) the photocatalyst has ferroelectricity, and an internal electric field generated by spontaneous polarization of the photocatalyst can improve the separation of photo-generated electrons and holes and prevent recombination.
(2) The invention adopts a simple solid phase reaction method to synthesize the powder, can inhibit the generation of impure phases and prepare pure-phase powder.
(3) The photocatalyst is nano-scale, can shorten the time for a current carrier to migrate to a reaction site, and improves the reaction activity.
(4) After the photocatalyst is subjected to high-energy ball milling through a WC tank, the surfaces of particles are wrapped by WC, and the WC serving as a cocatalyst can effectively prevent the recombination of photoproduction electrons and holes, so that the photocatalytic efficiency is further improved.
(5) The photocatalyst can be widely used in the fields of hydrogen production by photolysis of water, organic matter degradation and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of a sample prepared in example 2;
FIG. 3 is an X-ray diffraction pattern of a sample prepared in example 3;
FIG. 4 is an X-ray diffraction pattern of the sample prepared in comparative example 1;
FIG. 5 is a transmission electron micrograph of a sample prepared in example 3;
FIG. 6 is T of a sample obtained in example 2cA curve;
FIG. 7 is a PE-IE curve for the sample prepared in example 2;
fig. 8 shows the forbidden band widths of the samples prepared in example 1, example 2 and comparative example 1.
FIG. 9 is the light absorption spectra of RhB solutions of the samples prepared in example 3 under different illumination times.
Detailed description of the preferred embodiments
The invention is further illustrated by, but is not limited to, the following examples.
Rhodamine B (RhB) photocatalytic degradation rate: preparing 10ppm RhB solution, taking 50ml as experimental solution, adding 150mg sample, and stirring for 30min on a magnetic stirrer. Sampling at 30min intervals with 300W xenon lamp as light source, placing in dark, centrifuging after 8 times, collecting supernatant, and measuring absorbance.
Analysis of ferroelectricity: sintering the sample at 900-1000 ℃ to obtain the ceramic sample. After a ceramic sample is ground, polished and silvered, an LCR tester is adopted to measure the change of dielectric constant and loss along with temperature; and measuring the ferroelectric hysteresis loop of the material by adopting a ferroelectric tester.
Optical performance analysis: and measuring the light absorption curve of the sample by using a UV-Vis spectrometer, and calculating the bandwidth of the sample by using a Tauc formula.
Example 1
(1) Will Rb2CO3、BiO2And Nb2O5According to the chemical formula RbBiNb2O7Compounding, wherein Rb2CO3Adding the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours by using a planetary ball mill at the rotating speed of 150r/min, drying for 12 hours on a hot bench at the temperature of 80 ℃, and sieving to obtain mixed powder for later use;
(2) placing the mixed powder in a box furnace, preserving heat for 4h at 1000 ℃, taking out, dry-grinding for 4h under the condition that the rotating speed is 100r/min, and repeatedly preserving heat and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) putting the synthetic powder into a nylon ball milling tank, wherein the milling ball is ZrO2And (3) ball milling the spheres with absolute ethyl alcohol as a dispersion medium at a high energy for 24 hours at a rotating speed of 360r/min, and drying and sieving the spheres to obtain the nano powder.
As shown in FIG. 1, the obtained RbBiNb2O7The nanopowder is a single phase with a cubic crystal structure and a space group of P21am; the average laser particle size of the powder was 400 nm.
The powder is shaped and sintered (sintering temperature: 1000 ℃) and then is tested for ferroelectric and dielectric properties, the Curie temperature is 1071 ℃, which shows that the material has ferroelectric property, and the bandwidth of the powder is calculated to be 3.35 eV.
A sample is subjected to a photocatalytic degradation organic dye (rhodamine B) test, the degradation rate of RhB after 4 hours of illumination is 30%, and the degradation rate is 0.1111 k/h.
Example 2
(1) Will Rb2CO3、BiO2、Nb2O5And TiO2According to the chemical formula RbBi2Ti2NbO10Compounding, wherein Rb2CO3Adding the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours by using a planetary ball mill at the rotating speed of 150r/min, drying for 12 hours on a hot bench at the temperature of 80 ℃, and sieving to obtain mixed powder for later use;
(2) placing the mixed powder in a box furnace, preserving heat for 4h at 950 ℃, taking out, dry-grinding for 4h under the condition that the rotating speed is 60r/min, and repeatedly preserving heat and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) and (3) putting the synthetic powder into a nylon ball milling tank, performing high-energy ball milling for 24 hours at the rotating speed of 360r/min by using absolute ethyl alcohol as a dispersion medium, and drying and sieving to obtain the nano powder.
As shown in FIG. 2, the prepared RbBi2Ti2NbO10The nano powder is a single phase, the crystal structure is a cubic phase, and the space group is Ima 2; the average laser particle size of the powder was 400 nm.
As shown in FIG. 6 and FIG. 7, the powder is sintered (sintering temperature: 950 ℃) and then tested for ferroelectric and dielectric properties, the Curie temperature is 506 ℃, and the bandwidth of the powder is calculated to be 3.25 eV; the IE curve shows a current peak to indicate that the ferroelectric domain in the material is reversed, and the prepared RbBi2Ti2NbO10Is a ferroelectric material.
A sample is subjected to a photocatalytic degradation organic dye (rhodamine B) test, the degradation rate of RhB after 4 hours of illumination is 65%, and the degradation rate is 0.2147 k/h.
Example 3
(1) Will Rb2CO3、BiO2、Nb2O5And TiO2According to the chemical formula RbBi2Ti2NbO10Compounding, wherein Rb2CO3Adding the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours by using a planetary ball mill at the rotating speed of 150r/min, drying for 12 hours on a hot bench at the temperature of 80 ℃, and sieving to obtain mixed powder for later use;
(2) placing the mixed powder in a box furnace, preserving heat for 4h at 950 ℃, taking out, dry-grinding for 4h under the condition that the rotating speed is 60r/min, and repeatedly preserving heat and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) putting the synthetic powder into a WC ball milling tank, taking deionized water as a dispersion medium, carrying out high-energy ball milling for 1h at the rotating speed of 800r/min, and drying and sieving to obtain the nano powder.
As shown in FIG. 3, the obtained nanopowder is RbBi2Ti2NbO10、ZrO2And a mixture of three phases WC.
As shown in FIG. 5, the average particle size of the nanopowder obtained by high-energy ball milling of the synthetic powder is 50-80 nm.
As shown in FIG. 9, the sample was subjected to photocatalytic degradation of organic dye (rhodamine B) test, and the degradation rate of RhB after 2h of illumination was 100% and 1.06 k/h.
Comparative example 1
(1) Will Rb2CO3、BiO2And Nb2O5According to the chemical formula RbBi4Nb5O16Compounding, wherein Rb2CO3Adding the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours by using a planetary ball mill at the rotating speed of 150r/min, drying for 12 hours on a hot bench at the temperature of 80 ℃, and sieving to obtain mixed powder for later use;
(2) placing the mixed powder in a box furnace, preserving heat for 4h at 975 ℃, taking out, dry-grinding for 4h under the condition that the rotating speed is 100r/min, and repeatedly preserving heat and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) and putting the synthetic powder into a nylon ball milling tank, performing high-energy ball milling for 12 hours at the rotation speed of 400r/min by using absolute ethyl alcohol as a dispersion medium, and drying and sieving to obtain the nano powder.
As shown in fig. 4, the synthesized nanopowder is a single phase, the crystal structure is cubic phase, the space group is Fd3m, and it is a non-ferroelectric phase; the average laser particle size of the powder was 380 nm.
After the powder is formed and sintered (sintering temperature: 1050 ℃), ferroelectric and dielectric property tests are carried out, Curie peaks and current peaks are not found, which indicates that the material is a non-ferroelectric phase and is consistent with XRD results. The bandwidth of the powder was calculated to be 3.02 eV.
And (3) carrying out a photocatalytic degradation organic dye (rhodamine B) test on the sample, wherein the degradation rate of RhB after illumination for 4h is 20%, and the degradation rate is 0.0402 k/min.
Claims (7)
1. A photocatalyst having ferroelectricity, characterized in that: the structural general formula of the photocatalyst is RbBin- 1BnO3n+1Wherein the metal B is Nb or Nb and Ti, and n is more than or equal to 2 and less than or equal to 4.
2. The photocatalyst having ferroelectricity according to claim 1, characterized in that: the metal B is Nb and Ti, and the molar ratio of Nb to Ti is 1: 2, n is 3.
3. The photocatalyst having ferroelectricity according to claim 1, characterized in that: the surface of the photocatalyst is also wrapped with WC, and RbBi is obtained byn-1BnO3n+1Placing the mixture in a WC tank for high-energy ball milling to obtain the product.
4. The method for preparing the photocatalyst having ferroelectricity according to any one of claims 1 to 3, comprising the steps of:
(1) will Rb2CO3、BiO2And an oxide of metal B, wherein Rb is mixed according to a set molar ratio2CO3Excessive amount is 1-5 wt%, and the mixed powder is obtained by wet grinding and drying for later use;
(2) carrying out solid-phase synthesis on the mixed powder obtained in the step (1) at high temperature, then carrying out dry grinding, and repeating the solid-phase synthesis for 1-2 times to obtain synthetic powder for later use;
(3) and (3) performing ball milling on the synthetic powder obtained in the step (2) to obtain nanoscale sample powder.
5. The method for preparing a photocatalyst having ferroelectricity according to claim 4, wherein: in the step (1), the wet grinding process parameters are as follows: the ball milling tank is a nylon tank, the ball milling medium is alcohol, the rotating speed is 100-; the drying temperature is 80-100 deg.C, and the drying time is 8-12 h.
6. The method for preparing a photocatalyst having ferroelectricity according to claim 4, wherein: in the step (2), the temperature of solid phase synthesis is 850-1000 ℃, and the time is 4-24 h; the dry milling process parameters are as follows: the rotating speed is 50-100rmp, and the ball milling time is 2-6 h.
7. The method for preparing a photocatalyst having ferroelectricity according to claim 4, wherein: in the step (3), the ball milling mode is common ball milling, and the technological parameters are as follows: the ball milling tank is a nylon tank, and the grinding ball is ZrO2Ball, the ball milling medium is alcohol, the rotating speed is 300-n-1BnO3n+1；
Or the ball milling mode is high-energy ball milling, and the technological parameters are as follows: the ball milling tank is a WC tank, and the grinding balls are ZrO2The ball milling medium is water, the rotating speed is 800-n- 1BnO3n+1。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017504A (en) * | 1998-07-16 | 2000-01-25 | Universite Laval | Process for synthesizing perovskites using high energy milling |
| CN101745378A (en) * | 2010-01-02 | 2010-06-23 | 桂林理工大学 | Visible-light response composite oxide photocatalyst Li9Ti5Nb5-xTaxO27 and preparation method thereof |
| CN102247894A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rhodamine B-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN105170157A (en) * | 2015-09-21 | 2015-12-23 | 中国计量学院 | Neodymium-doped bismuth ferrite nanometer photocatalyst and preparation method thereof |
| CN106011927A (en) * | 2016-07-29 | 2016-10-12 | 西安电子科技大学 | P-type semiconductor visible light photocatalytic material and hydrogen production method |
| CN107759219A (en) * | 2017-11-14 | 2018-03-06 | 广州光鼎科技有限公司 | A kind of high curie temperature leadless piezoelectric ceramal and preparation method thereof |
| CN109745992A (en) * | 2018-12-04 | 2019-05-14 | 信阳师范学院 | A kind of single-phase Ferroelectic Nanomaterials of highlight catalytic active and preparation method thereof |
| CN110015894A (en) * | 2019-05-06 | 2019-07-16 | 广州光鼎科技集团有限公司 | The bismuth-sodium titanate base ceramics and its preparation method and application of dielectric stable under a kind of high temperature |
-
2020
- 2020-06-10 CN CN202010521244.XA patent/CN111604047B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017504A (en) * | 1998-07-16 | 2000-01-25 | Universite Laval | Process for synthesizing perovskites using high energy milling |
| CN101745378A (en) * | 2010-01-02 | 2010-06-23 | 桂林理工大学 | Visible-light response composite oxide photocatalyst Li9Ti5Nb5-xTaxO27 and preparation method thereof |
| CN102247894A (en) * | 2011-05-26 | 2011-11-23 | 东北大学 | Rhodamine B-doped modified titanium concentrate photocatalyst and preparation method thereof |
| CN105170157A (en) * | 2015-09-21 | 2015-12-23 | 中国计量学院 | Neodymium-doped bismuth ferrite nanometer photocatalyst and preparation method thereof |
| CN106011927A (en) * | 2016-07-29 | 2016-10-12 | 西安电子科技大学 | P-type semiconductor visible light photocatalytic material and hydrogen production method |
| CN107759219A (en) * | 2017-11-14 | 2018-03-06 | 广州光鼎科技有限公司 | A kind of high curie temperature leadless piezoelectric ceramal and preparation method thereof |
| CN109745992A (en) * | 2018-12-04 | 2019-05-14 | 信阳师范学院 | A kind of single-phase Ferroelectic Nanomaterials of highlight catalytic active and preparation method thereof |
| CN110015894A (en) * | 2019-05-06 | 2019-07-16 | 广州光鼎科技集团有限公司 | The bismuth-sodium titanate base ceramics and its preparation method and application of dielectric stable under a kind of high temperature |
Non-Patent Citations (4)
| Title |
|---|
| HYUNG GU KIM ET.AL: "Two New Non-centrosymmetric (NCS) n = 3 Layered Dion-Jacobson (DJ) Perovskites: Polar RbBi2Ti2NbO10 and Nonpolar CsBi2Ti2TaO10", 《CHEMISTRY OF MATERIALS》 * |
| MOHAMMAD GHAFFARI ET.AL: "Effect of ball milling on the characteristics of nano structure SrFeO3 powder for photocatalytic degradation of methylene blue under visible light irradiation and its reaction kinetics", 《CATALYSIS TODAY》 * |
| TETSUYA KAKO ET.AL: "Photocatalytic Decomposition of Acetaldehyde over Rubidium Niobates under Visible Light Irradiation", 《MATERIALS TRANSACTIONS》 * |
| 魏月琳等: "钽掺杂对层状钙钛矿镧钛酸钾光催化性能的影响", 《材料研究学报》 * |
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