CN111604047B - 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 27
- 230000005621 ferroelectricity Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 38
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 11
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 13
- 238000009837 dry grinding Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000004677 Nylon Substances 0.000 claims description 10
- 229920001778 nylon Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 15
- 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 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 101100233056 Caenorhabditis elegans ima-2 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 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
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 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
Classifications
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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
-
- 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 structural general formula of the photocatalyst is RbBi n‑1 B n O 3n+1 Wherein 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 photocatalyst with nano-scale particle size is obtained through simple solid phase synthesis and ball milling. The photocatalyst of the invention is nano-scale and can shorten carrier migrationThe time to the reaction site increases the reactivity; the device has ferroelectricity, and an internal electric field generated by spontaneous polarization can improve the separation of photo-generated electrons and holes and prevent recombination; the surface of the catalyst can be further wrapped by a cocatalyst WC through high-energy ball milling, and the photocatalytic efficiency is high.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and relates to a photocatalyst with ferroelectricity and a preparation method thereof.
Background
Photocatalytic materials have been studied for nearly fifty years, and titanium dioxide (TiO was found and reported from the first 1972 japanese researchers 2 ) Since photocatalytic materials are used for photocatalytic water splitting, researchers have been working on improving the light conversion efficiency of existing materials and searching for new high performance materials. The photocatalysts commonly used at present are oxide semiconductors such as titanium dioxide, zinc oxide, tin oxide, zirconium dioxide and the like. However, in general, the oxide catalyst material has a large forbidden bandwidth, and the sulfide catalyst has a small forbidden bandwidth but has unstable chemical properties, and these disadvantages limit the application of the sulfide catalyst material in the field of photocatalysis. Therefore, the modification of the photocatalyst and the development of a novel catalyst are now the hot spot directions for the research of the photocatalysis technology.
The photocatalysis process mainly comprises the following three steps: absorption of light energy, separation and migration of photogenerated electrons and holes, surface adsorption and reaction. In recent years, ferroelectric materials have been attracting attention as novel photocatalytic materials. On the one hand, the ferroelectric material forms an internal electric field due to spontaneous polarization, so that separation of electrons and holes in a photocatalytic reaction is promoted; on the other hand, the depolarization field inside the ferroelectric material can cause band bending, resulting in a spatially selective reaction. Ferroelectricity is beneficial to improving the photocatalytic performance of materials, and has been described in barium titanate (BaTiO 3 ) Bismuth ferrite (BiFeO) 3 ) Lead zirconate titanate (Pb (Zr) 0.3 Ti 0.7 )O 3 ) And the like. The shape of the photocatalytic material is controlled, and the photocatalytic efficiency can be effectively improved by using the cocatalyst. The nano material has higher specific surface energy, more reaction sites and higher reaction activity; meanwhile, due to the small particle size of the nano material, the path from the carrier to the particle is shorter, the compounding probability is low, and the higher photocatalytic performance is facilitated. On the other hand, the promoters commonly used at present are noble metals such as Pt, rh and Ru, but these materials are not widely used because of their high price.
In summary, the existing photocatalytic material has the defect of low photocatalytic efficiency caused by easy recombination of photo-generated electrons and holes, so that it is important to develop a catalyst with high catalytic activity and a preparation method thereof.
Disclosure of Invention
Aiming at the defect of low photocatalytic efficiency caused by easy recombination of photo-generated electrons and holes in the existing photocatalytic material, the invention aims to provide the photocatalyst with ferroelectricity and the preparation method thereof, and the photocatalyst with the particle size of nanometer is obtained through simple solid phase synthesis and ball milling, the surface of the photocatalyst can be further wrapped by a cocatalyst WC through high-energy ball milling, and the physical and structural characteristics of the photocatalyst can effectively promote separation of the photo-generated electrons and the holes, prevent recombination and have high photocatalytic efficiency.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a photocatalyst with ferroelectricity has a general structural formula of RbBi n-1 B n O 3n+1 Wherein 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 mole ratio of Nb to Ti is 1:2, n=3.
Preferably, the photocatalyst surface is further coated with WC by coating RbBi n-1 B n O 3n+1 Placing the mixture in a WC tank for high-energy ball milling.
The invention also provides a preparation method of the photocatalyst, which comprises the following steps:
(1) Rb 2 CO 3 、BiO 2 And metal B oxide in a set molar ratio, wherein Rb 2 CO 3 Excessive 1-5 wt%, wet milling and drying to obtain mixed powder;
(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) ball milling the synthesized powder obtained in the step (2) to obtain nanoscale sample powder.
Preferably, 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 100-200rmp, and the ball milling time is 2-6h; the drying temperature is 80-100deg.C, and the drying time is 8-12 hr.
In the step (2), the solid phase synthesis temperature is 850-1000 ℃ and the time is 4-24 hours; the dry grinding process parameters are as follows: the rotating speed is 50-100rmp, and the ball milling time is 2-6h.
In the preferred 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 nylon tank, and the grinding ball is ZrO 2 Ball, ball milling medium is alcohol, rotating speed is 300-400r/min, ball milling time is 20-40h, and nano RbBi is obtained n-1 B n O 3n+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 ZrO 2 Ball milling medium is water, the rotating speed is 800-1000r/min, each ball milling is stopped for 1min for 2min, the time is 1-4h, and the nano WC@RbBi is obtained n-1 B n O 3n+1 . The inventor surprisingly found that by placing the synthesized powder after solid phase synthesis in a WC tank for high-energy ball milling, the surface of the synthesized powder can be wrapped by WC, and WC can be used as a cocatalyst, so that the recombination 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 of the invention has ferroelectricity, and the internal electric field generated by spontaneous polarization 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 powder, can inhibit the generation of mixed phases, and prepares pure-phase powder.
(3) The photocatalyst is nano-scale, can shorten the time for carrier migration to a reaction site, and improves the reaction activity.
(4) After the photocatalyst is subjected to high-energy ball milling through the WC pot, the particle surfaces are wrapped by WC, and the WC serving as a cocatalyst can effectively prevent the recombination of photo-generated electrons and holes, so that the photocatalysis efficiency is further improved.
(5) The photocatalyst of the invention can be widely used in the fields of hydrogen production by photocatalytic water splitting, 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 the sample prepared in example 2;
FIG. 3 is an X-ray diffraction pattern of the 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 microscope image of the sample prepared in example 3;
FIG. 6 is a T-plot of the sample obtained in example 2 c A curve;
FIG. 7 is a PE-IE curve of the sample prepared in example 2;
fig. 8 shows the forbidden bandwidths of the samples prepared in example 1, example 2 and comparative example 1.
FIG. 9 is a graph showing the light absorption spectrum of RhB solution of the sample prepared in example 3 under different illumination times.
Detailed description of the preferred embodiments
The invention is further illustrated, but not limited, by the following examples.
Rhodamine B (RhB) photocatalytic degradation rate: 10ppm of RhB solution was prepared, 50ml of the solution was taken as an experimental solution, 150mg of the sample was placed in the solution, and the solution was stirred on a magnetic stirrer for 30 minutes. Taking 300W xenon lamp as light source, sampling every 30min, placing in dark place, centrifuging after 8 times, collecting supernatant, and measuring absorbance.
Ferroelectricity analysis: sintering the sample at 900-1000 ℃ to obtain the ceramic sample. Polishing, polishing and silver coating the ceramic sample, and measuring the dielectric constant and the change of loss along with the temperature by adopting an LCR tester; ferroelectric tester is used to measure the hysteresis loop of the material.
Analysis of optical Properties: the light absorption curve of the sample was measured with a UV-Vis spectrometer and the bandwidth of the sample was calculated using the Tauc formula.
Example 1
(1) Rb 2 CO 3 、BiO 2 And Nb (Nb) 2 O 5 According to the chemical formula RbBiNb 2 O 7 Dispensing, wherein Rb 2 CO 3 Placing the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours under the condition of 150r/min of rotating speed by a planetary ball mill, drying for 12 hours on a hot table at 80 ℃, and sieving to obtain mixed powder for later use;
(2) Placing the mixed powder into a box furnace, preserving heat for 4 hours at 1000 ℃, taking out, dry-grinding for 4 hours at the rotating speed of 100r/min, and repeating the temperature and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) Putting the synthesized powder into a nylon ball milling tank, wherein the grinding balls are ZrO 2 Ball milling is carried out for 24h under the condition of 360r/min rotation speed by taking absolute ethyl alcohol as a dispersion medium, and nano powder is obtained after drying and sieving.
As shown in FIG. 1, the RbBiNb was prepared 2 O 7 The nano powder is single-phase, the crystal structure is cubic phase, and the space group is P2 1 am; the average laser particle size of the powder was 400nm.
After the powder is formed and sintered (sintering temperature: 1000 ℃) is subjected to ferroelectric and dielectric property test, the Curie temperature is 1071 ℃, the material has ferroelectricity, and the bandwidth of the powder is calculated to be 3.35eV.
The sample is subjected to a photocatalytic degradation organic dye (rhodamine B) test, the degradation rate of the sample on RhB after illumination for 4 hours is 30%, and the degradation rate is 0.1111k/h.
Example 2
(1) Rb 2 CO 3 、BiO 2 、Nb 2 O 5 And TiO 2 According to the chemical formula RbBi 2 Ti 2 NbO 10 Dispensing, wherein Rb 2 CO 3 Placing the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours under the condition of 150r/min of rotating speed by a planetary ball mill, drying for 12 hours on a hot table at 80 ℃, and sieving to obtain mixed powder for later use;
(2) Placing the mixed powder into a box furnace, preserving heat for 4 hours at 950 ℃, taking out, dry-grinding for 4 hours at the rotating speed of 60r/min, and repeating the temperature and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) Putting the synthesized powder into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, performing high-energy ball milling for 24 hours under the condition of 360r/min rotating speed, and drying and sieving to obtain the nano powder.
As shown in FIG. 2, the obtained RbBi 2 Ti 2 NbO 10 The nano powder is a single phase, the crystal structure is a cubic phase, and the space group is Ima2; the average laser particle size of the powder was 400nm.
As shown in fig. 6 and 7, after the powder was molded and sintered (sintering temperature: 950 ℃) and tested for ferroelectric and dielectric properties, the curie temperature was measured to be 506 ℃, and the bandwidth of the powder was calculated to be 3.25eV; the IE curve shows a current peak, which indicates that the material has ferroelectric domain inside to turn over, and the prepared RbBi 2 Ti 2 NbO 10 Is a ferroelectric material.
The sample is subjected to a photocatalytic degradation organic dye (rhodamine B) test, the degradation rate of the sample on RhB after illumination for 4 hours is 65%, and the degradation rate is 0.2147k/h.
Example 3
(1) Rb 2 CO 3 、BiO 2 、Nb 2 O 5 And TiO 2 According to the chemical formula RbBi 2 Ti 2 NbO 10 Dispensing, wherein Rb 2 CO 3 Adding the mixture into nylon ball milling tank, taking absolute ethanol as dispersion medium, ball milling with planetary ball mill at 150r/min for 4 hr, and heating at 80deg.CDrying for 12h, and sieving to obtain mixed powder for later use;
(2) Placing the mixed powder into a box furnace, preserving heat for 4 hours at 950 ℃, taking out, dry-grinding for 4 hours at the rotating speed of 60r/min, and repeating the temperature and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) Putting the synthesized powder into a WC ball milling tank, taking deionized water as a dispersion medium, performing high-energy ball milling for 1h under the condition of the rotating speed of 800r/min, and drying and sieving to obtain the nano powder.
As shown in FIG. 3, the obtained nano powder is RbBi 2 Ti 2 NbO 10 、ZrO 2 And WC three phase mixtures.
As shown in FIG. 5, the average particle size of the nano powder obtained by high-energy ball milling of the synthetic powder is 50-80 nm.
As shown in FIG. 9, the sample was subjected to a photocatalytic degradation organic dye (rhodamine B) test, and the degradation rate of RhB after 2 hours of illumination was 100%, and the degradation rate was 1.06k/h.
Comparative example 1
(1) Rb 2 CO 3 、BiO 2 And Nb (Nb) 2 O 5 According to the chemical formula RbBi 4 Nb 5 O 16 Dispensing, wherein Rb 2 CO 3 Placing the mixture into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, ball milling for 4 hours under the condition of 150r/min of rotating speed by a planetary ball mill, drying for 12 hours on a hot table at 80 ℃, and sieving to obtain mixed powder for later use;
(2) Placing the mixed powder into a box furnace, preserving heat for 4 hours at 975 ℃, taking out, dry-grinding for 4 hours at the rotating speed of 100r/min, and repeatedly carrying out the temperature and dry-grinding for 2 times to obtain pure-phase synthetic powder for later use;
(3) Putting the synthesized powder into a nylon ball milling tank, taking absolute ethyl alcohol as a dispersion medium, performing high-energy ball milling for 12 hours under the condition of 400r/min of rotating speed, and drying and sieving to obtain the nano powder.
As shown in fig. 4, the synthesized nano powder is a single phase, the crystal structure is a cubic phase, the space group is Fd3m, and the synthesized nano powder is a non-ferroelectric phase; the average laser particle size of the powder was 380nm.
After the powder is formed and sintered (sintering temperature: 1050 ℃) and ferroelectric and dielectric properties are tested, 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 3.02eV.
The sample is subjected to a photocatalytic degradation organic dye (rhodamine B) test, the degradation rate of the sample on RhB after 4 hours of illumination is 20%, and the degradation rate is 0.0402k/min.
Claims (4)
1. A photocatalyst having ferroelectricity, characterized in that: the structural general formula of the photocatalyst is WC@RbBi n- 1 B n O 3n+1 Wherein the metal B is Nb, or Nb and Ti, n is more than or equal to 2 and less than or equal to 4; the preparation process of the photocatalyst comprises the following steps: (1) Rb 2 CO 3 、BiO 2 And metal B oxide in a set molar ratio, wherein Rb 2 CO 3 Excessive 1-5 wt%, wet milling and drying to obtain mixed powder; (2) Carrying out solid phase synthesis on the mixed powder obtained in the step (1) at a 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) Ball milling the synthesized powder obtained in the step (2) to obtain nanoscale sample powder;
in the step (3), 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 ZrO 2 Ball milling medium is water, the rotating speed is 800-1000r/min, each ball milling time is 1min after 2min, the time is 1-4h, and the nano WC@RbBi is obtained n-1 B n O 3n+1 。
2. The photocatalyst having ferroelectricity according to claim 1, wherein: the metal B is Nb and Ti, and the mole ratio of Nb to Ti is 1:2, n=3.
3. The photocatalyst having ferroelectricity according to claim 1, 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 100-200 rpm, and the ball milling time is 2-6h; the drying temperature is 80-100 ℃ and the drying time is 8-12h.
4. The photocatalyst having ferroelectricity according to claim 1, wherein: in the step (2), the solid phase synthesis temperature is 850-1000 ℃ and the time is 4-24 hours; the dry grinding process parameters are as follows: the rotating speed is 50-100 rpm, and the ball milling time is 2-6h.
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