CN112516990A - Synthetic method and application of layered perovskite type photocatalyst - Google Patents
Synthetic method and application of layered perovskite type photocatalyst Download PDFInfo
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- CN112516990A CN112516990A CN202011525565.3A CN202011525565A CN112516990A CN 112516990 A CN112516990 A CN 112516990A CN 202011525565 A CN202011525565 A CN 202011525565A CN 112516990 A CN112516990 A CN 112516990A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 238000010189 synthetic method Methods 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 7
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000001308 synthesis method Methods 0.000 claims description 7
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000007790 solid phase Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000000969 carrier Substances 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
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- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 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
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- 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
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- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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 method for synthesizing a layered perovskite type photocatalyst, which comprises the following steps: (1) mixing SrCl2·6H2Dissolving O, a bismuth source and tetrabutyl titanate in a nitric acid solution to obtain a raw material solution; (2) dripping the obtained raw material liquid into a sodium hydroxide solution, and then carrying out hydrothermal synthesis to obtain a white suspension; (3) cooling and filtering the suspension, taking filter residue, washing and drying the filter residue to obtain the layered perovskite Sr2Bi4Ti5O18. Also discloses the application of the layered perovskite photocatalyst in photocatalytic reaction. The preparation process is simple, the reaction controllability is good, and the formed layered perovskite type Sr2Bi4Ti5O18Strong light absorption capacity, wide light absorption range, high activity of photon-generated carriers and strong photocatalytic hydrogen production capacity compared with the traditional TiO2More than 3.2 times of that of the solid phase sintering synthesis, more than 2.8 times of that of the solid phase sintering synthesis, and is Bi4Ti3O12More than 2 times of the total weight of the composition.
Description
Technical Field
The invention relates to a synthesis method and application of a layered perovskite type photocatalyst, and belongs to the field of photocatalysts.
Background
With the continuous increase of the world population and the rapid development of industrialization, the energy consumption and the energy demand are high, and the two problems of energy crisis and environmental pollution caused by the high energy consumption and the high energy demand are more and more noticed. In recent years, photocatalytic technology has been rapidly developed, and pollutant decomposition efficiency and hydrogen production efficiency have been continuously improved. However, at present, most of semiconductor materials have short photon-generated carrier life and short average diffusion length, and the photon-generated electron hole pair has low separation efficiency and low photocatalytic activity, and the photocatalytic performance of the semiconductor materials can not meet the requirements of practical application.
The perovskite material has high light absorption rate and energy conversion efficiency in a visible light range, and has good application prospect in the production of renewable energy sources such as photovoltaics, photocatalysis and the like. Sr2Bi4Ti5O18Located at the cross point of the traditional ferroelectric, laminated bismuth-based semiconductor and perovskite structure crystal, integrates a plurality of advantages and shows great photocatalytic potential. However, at present, to Sr2Bi4Ti5O18The research is mainly focused on the application of the ferroelectric ceramic, and the ferroelectric ceramic is not applied to the field of photocatalysis.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for synthesizing a layered perovskite photocatalyst, the layered perovskite photocatalyst having the chemical formula: sr2Bi4Ti5O18(ii) a The synthesis method comprises the following steps:
(1) mixing SrCl2·6H2Source of O, bismuthDissolving tetrabutyl titanate in a nitric acid solution to obtain a raw material solution;
(2) dripping the obtained raw material liquid into a sodium hydroxide solution, and then carrying out hydrothermal synthesis to obtain a white suspension;
(3) cooling and filtering the suspension, taking filter residue, washing and drying the filter residue to obtain the layered perovskite Sr2Bi4Ti5O18。
In the step (2), after the dropwise addition of the raw material liquid to the sodium hydroxide solution is completed, the stirring is continued for 30-120 minutes, so that the reaction is fully performed, and simultaneously, the reaction heat can be discharged in time, thereby avoiding the influence on the smooth performance of the subsequent hydrothermal reaction due to the excessive heat released during the acid-base neutralization reaction. The strong basicity of the concentrated sodium hydroxide solution hydrolyzes tetrabutyl titanate into dissolved titanate, and the uniform reaction solution is favorable for the formation of a nano structure. Further hydrothermal reaction makes the reactant dissolve-recrystallize to reach atom level uniform mixing.
Specifically, the bismuth source is bismuth nitrate or bismuth sulfate.
The preparation process is simple, the reaction controllability is good, and the formed layered perovskite type Sr2Bi4Ti5O18Strong light absorption capacity, wide light absorption range, high activity of photon-generated carriers and strong photocatalytic hydrogen production capacity compared with the traditional TiO2More than 3.2 times of that of the solid phase sintering synthesis, more than 2.8 times of that of the solid phase sintering synthesis, and is Bi4Ti3O12More than 2 times of the total weight of the composition.
Sr2Bi4Ti5O18Is a typical bismuth-layer perovskite structure ferroelectric material, and has the basic structural characteristics that a fluorite structure bismuth oxide layer (Bi) is inserted into 5 perovskite layers2O2)2+Due to the insertion of the bismuth-oxygen layer, the material system shows obvious anisotropy, and the anisotropy causes the material system to tend to form a nanosheet shape with high surface area in the process of synthesis and preparation; the valence band energy level of the photocatalyst consists of highly discrete Bi 6s and O2 p hybrid orbitals, and the highly discrete orbital energy level is more beneficial to the migration of photo-generated holes and corresponding photocatalytic oxidation reaction. And due to bismuth oxygenPresence of a layer such that Sr2Bi4Ti5O18Has very high structure and performance adjustability. Reasonably utilizing doping and other means can probably improve the ferroelectric property to a certain extent, which is very beneficial to effectively separating photon-generated carriers and improving the photocatalytic activity, but the prior Sr is2Bi4Ti5O18The product can not be used as a photocatalyst.
The existing Sr is found through experiments2Bi4Ti5O18The product is mainly applied to ferroelectric ceramics, Sr2Bi4Ti5O18The production of (A) is synthesized by high-temperature solid-phase reaction, which results in larger particle size of the product, insufficient effective reaction point, failure of effective absorption of photons and generation of photon-generated carriers. Sr produced by hydrothermal synthesis method2Bi4Ti5O18The product has proper forbidden band width and nano structure, can effectively absorb photons to the maximum extent and generate photon-generated carriers, thereby having the function of photocatalyst. Compared with solid-phase sintered crystals, the hydrothermal synthesis has less growth defects and good orientation, and the proper size effectively reduces the recombination of photoproduction electrons and holes, namely Sr2Bi4Ti5O18The spontaneous ferroelectric polarization further promotes the separation and migration of photo-generated electrons and holes, and greatly increases the photocatalytic performance of the photo-generated electrons.
Specifically, the temperature of the hydrothermal synthesis is 180-240 ℃, and the time is 24-72 h. Under the condition, the synthesized Sr2Bi4Ti5O18Presenting a sheet-like morphology. In the temperature and time range, Sr is favored2Bi4Ti5O18The synthesis of (2) and the reduction of the generation of miscellaneous items, and the improvement of the crystallinity along with the increase of the temperature and the prolongation of the time.
Specifically, the concentration of the nitric acid solution is 4-5mol/L, and the concentration of the sodium hydroxide solution is 6-9 mol/L. The volume ratio of the nitric acid solution to the sodium hydroxide solution is 1:1-1: 1.2.
At the concentration of the nitric acid solution, the metal ions can be dissolved rapidly and sufficiently, but the layered calciumTitanium ore type Sr2Bi4Ti5O18Cannot be synthesized under the acidic condition, and in order to compensate the defect, the sodium hydroxide with the concentration is used for providing a strong alkaline environment required by the reaction so as to obtain the desired product. The desired product can be obtained within the limits of the nitric acid solution concentration, the sodium hydroxide solution concentration and the volume ratio of the nitric acid solution to the sodium hydroxide solution. When the alkali concentration is insufficient or the alkali is excessive, the product has excessive impurities, which is not beneficial to obtaining pure phase products.
The volume ratio of the nitric acid solution to the sodium hydroxide solution also plays a role in absorbing reaction heat in time under the condition of ensuring that the effective alkali concentration is improved, and the sufficient volume of the solution can absorb the reaction heat in time, so that the solution volatilization and the high-temperature decomposition of some precursors in the solution caused by the sharp rise of the solution temperature in the dropping process are avoided.
Further, the drying temperature of the filter residue is 60-80 ℃, and the drying time is 7-10 h. After hydrothermal synthesis, the mixture is naturally cooled to room temperature and then filtered. At the temperature, the product after hydrothermal reaction can be dried quickly without affecting the structure of the product.
The layered perovskite type Sr as described in any one of the above2Bi4Ti5O18The photocatalyst is applied as a photocatalyst.
The invention provides the layered perovskite Sr2Bi4Ti5O18The preparation method of the photocatalyst has the advantages that the prepared photocatalyst is pure phase, has regular flaky shape, provides active sites for photocatalytic reaction, has better water decomposition performance than the traditional photocatalyst, has mild synthesis conditions, high product purity, complete crystal grain development, small grain size, uniform distribution, strong shape controllability and simple synthesis route and device, and is beneficial to realizing large-scale production.
Drawings
FIG. 1 is Sr synthesized in example 42Bi4Ti5O18X-ray diffraction (XRD) pattern of (a).
FIG. 2 shows Sr synthesized in example 42Bi4Ti5O18Scanning Electron Microscope (SEM) images of (a).
Detailed Description
Example 1
1. 30mL of 4mol/L nitric acid solution is measured and poured into a beaker according to Sr2Bi4Ti5O18Weighing 1.5mmol SrCl2·6H2O、1.5mmol Bi2(SO4)3And 3.75mmol of tetrabutyl titanate is dissolved in the nitric acid solution, and the mixture is stirred for 10min to obtain a raw material solution.
2. Weighing 7.2g NaOH and dissolving in 30mL deionized water, stirring for 5min, and cooling to room temperature to obtain sodium hydroxide solution.
3. Dropping the raw materials into the sodium hydroxide solution by using a dropper while stirring, stirring for 30min after the dropping is finished to uniformly mix the raw materials, transferring the mixture into a 100mL hydrothermal reaction kettle, and preserving the heat for 72h at the temperature of 180 ℃. After the reaction is finished, cooling the reaction liquid to normal temperature, centrifuging to take precipitate, washing 3 times by using ethanol and deionized water respectively, drying in a 60 ℃ oven for 10 hours, grinding into powder to prepare Sr2Bi4Ti5O18Photocatalyst 1 #.
And (3) detection:
40mg of Sr2Bi4Ti5O18Photocatalyst 1#, 40mg traditional photocatalyst TiO240mg of photocatalyst Bi4Ti3O12And 40mg of solid phase sintered Sr2Bi4Ti5O18Respectively putting into methanol solution to obtain four test solutions, irradiating with 500W medium-pressure mercury lamp for 5 hr, and measuring Sr2Bi4Ti5O18Photocatalyst No. 1 catalyzing to generate 16 mu mol H2，Bi4Ti3O12Photocatalyst catalyzed generation of 7.9 mu mol H2And solid phase sintering of synthesized Sr2Bi4Ti5O18Catalytic generation of H2 5.6μmol，TiO2Photocatalytic generation of H2Only 5. mu. mol. The methanol solution was mixed with 3ml of methanol and 30ml of deionized water.
Example 2
1. 28.4mL of 4.3mol/L nitric acid solution is weighed and poured into a beaker according to Sr2Bi4Ti5O18Weighing 1.5mmol SrCl2·6H2O、3mmol Bi(NO3)3·5H2Dissolving O and 3.75mmol tetrabutyl titanate in nitric acid solution, and stirring for 10min to obtain a raw material solution.
2. Weighing 8.4g NaOH and dissolving in 30mL deionized water, stirring for 5min, and cooling to room temperature to obtain sodium hydroxide solution.
3. Dropping the raw materials into the sodium hydroxide solution by using a dropper while stirring, stirring for 60min after the dropping is finished to uniformly mix the raw materials, transferring the mixture into a 100mL hydrothermal reaction kettle, and preserving the heat for 56h at the temperature of 200 ℃. After the reaction is finished, cooling the reaction liquid to normal temperature, centrifuging to take precipitate, washing 3 times by using ethanol and deionized water respectively, drying in a 67 ℃ oven for 9 hours, grinding into powder to prepare Sr2Bi4Ti5O18Photocatalyst 2 #.
And (3) detection:
40mg of Sr2Bi4Ti5O18Photocatalyst 2#, 40mg traditional photocatalyst TiO240mg of photocatalyst Bi4Ti3O12And 40mg of solid phase sintered Sr2Bi4Ti5O18Respectively putting into methanol solution to obtain four test solutions, irradiating with 500W medium-pressure mercury lamp for 5 hr, and measuring Sr2Bi4Ti5O18Photocatalyst 2# catalyzes and generates 15.4 mu mol H2，Bi4Ti3O12Photocatalyst catalyzed generation of 7.9 mu mol H2And solid phase sintering of synthesized Sr2Bi4Ti5O18Catalytic generation of H2 5.6μmol，TiO2Photocatalytic generation of H2Only 5. mu. mol. The methanol solution was mixed with 3ml of methanol and 30ml of deionized water.
Example 3
1. 26.7mL of 4.6mol/L nitric acid solution is weighed and poured into a beaker according to Sr2Bi4Ti5O18Is measured in a stoichiometric ratio1.5mmol SrCl2·6H2O、1.5mmol Bi2(SO4)3And 3.75mmol of tetrabutyl titanate is dissolved in the nitric acid solution, and the mixture is stirred for 10min to obtain a raw material solution.
2. Weighing 9.6g of NaOH and dissolving in 30mL of deionized water, stirring for 5min, and cooling to room temperature to obtain a sodium hydroxide solution.
3. Dropping the raw materials into the sodium hydroxide solution by using a dropper while stirring, stirring for 90min after the dropping is finished to uniformly mix the raw materials, transferring the mixture into a 100mL hydrothermal reaction kettle, and preserving the heat for 40h at 220 ℃. After the reaction is finished, cooling the reaction liquid to normal temperature, centrifuging to take precipitate, washing 3 times by using ethanol and deionized water respectively, drying in an oven at 73 ℃ for 8 hours, grinding into powder to prepare Sr2Bi4Ti5O18Photocatalyst # 3.
And (3) detection:
40mg of Sr2Bi4Ti5O18Photocatalyst 3#, 40mg traditional photocatalyst TiO240mg of photocatalyst Bi4Ti3O12And 40mg of solid phase sintered Sr2Bi4Ti5O18Respectively putting into methanol solution to obtain four test solutions, irradiating with 500W medium-pressure mercury lamp for 5 hr, and measuring Sr2Bi4Ti5O18Photocatalyst No. 3 catalyzes and generates 15.7 mu mol H2，Bi4Ti3O12Photocatalyst catalyzed generation of 7.9 mu mol H2And solid phase sintering of synthesized Sr2Bi4Ti5O18Catalytic generation of H2 5.6μmol，TiO2Photocatalytic generation of H2Only 5. mu. mol. The methanol solution was mixed with 3ml of methanol and 30ml of deionized water.
Example 4
1. 25mL of 5mol/L nitric acid solution is weighed and poured into a beaker according to Sr2Bi4Ti5O18Weighing 1.5mmol SrCl2·6H2O、3mmol Bi(NO3)3·5H2Dissolving O and 3.75mmol tetrabutyl titanate in nitric acid solution, and stirring for 10min to obtain raw materialAnd (4) feed liquid.
2. Weighing 10.8g of NaOH to be dissolved in 30mL of deionized water, stirring for 5min, and cooling to room temperature to obtain a sodium hydroxide solution.
3. Dropping the raw materials into the sodium hydroxide solution by using a dropper while stirring, stirring for 120min after the dropping is finished to uniformly mix the raw materials, transferring the mixture into a 100mL hydrothermal reaction kettle, and preserving the heat for 24h at the temperature of 240 ℃. After the reaction is finished, cooling the reaction liquid to normal temperature, centrifuging to take precipitate, washing 3 times by using ethanol and deionized water respectively, drying for 7 hours in an oven at 80 ℃, grinding into powder, and preparing Sr2Bi4Ti5O18Photocatalyst 4 #.
And (3) detection:
40mg of Sr2Bi4Ti5O18Photocatalyst 4#, 40mg traditional photocatalyst TiO240mg of photocatalyst Bi4Ti3O12And 40mg of solid phase sintered Sr2Bi4Ti5O18Respectively putting into methanol solution to obtain four test solutions, irradiating with 500W medium-pressure mercury lamp for 5 hr, and measuring Sr2Bi4Ti5O18Photocatalyst No. 4 catalyzed generation of 16.1. mu. mol H2，Bi4Ti3O12Photocatalyst catalyzed generation of 7.9 mu mol H2And solid phase sintering of synthesized Sr2Bi4Ti5O18Catalytic generation of H2 5.6μmol，TiO2Photocatalytic generation of H2Only 5. mu. mol. The methanol solution was mixed with 3ml of methanol and 30ml of deionized water.
The above examples show that the layered perovskite Sr prepared by the present application2Bi4Ti5O18The water decomposition performance of the photocatalyst is greatly superior to that of the traditional photocatalyst TiO2、Bi4Ti3O12Sr synthesized by photocatalyst and solid phase sintering2Bi4Ti5O18。
Claims (7)
1. A method for synthesizing a layered perovskite photocatalyst is characterized in that,
the layered perovskite type photocatalyst has a chemical formula as follows: sr2Bi4Ti5O18；
The synthesis method comprises the following steps:
(1) mixing SrCl2·6H2Dissolving O, a bismuth source and tetrabutyl titanate in a nitric acid solution to obtain a raw material solution;
(2) dripping the obtained raw material liquid into a sodium hydroxide solution, and then carrying out hydrothermal synthesis to obtain a white suspension;
(3) cooling and filtering the suspension, taking filter residue, washing and drying the filter residue to obtain the layered perovskite Sr2Bi4Ti5O18。
2. The synthesis method as claimed in claim 1, wherein the hydrothermal synthesis temperature is 180-240 ℃ and the time is 24-72 h.
3. The synthesis method according to claim 1, wherein the concentration of the nitric acid solution is 4-5mol/L, and the concentration of the sodium hydroxide solution is 6-9 mol/L.
4. The synthesis method according to claim 3, wherein the volume ratio of the nitric acid solution to the sodium hydroxide solution is 1:1-1: 1.2.
5. The method of synthesis of claim 1, wherein the bismuth source is bismuth nitrate or bismuth sulfate.
6. The synthesis method according to claim 1, wherein the drying temperature of the filter residue is 60-80 ℃ and the drying time is 7-10 h.
7. Use of a layered perovskite photocatalyst as defined in any one of claims 1 to 6 in photocatalytic reactions.
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| CN111545225A (en) * | 2020-04-17 | 2020-08-18 | 中国地质大学（北京） | Heterostructure photocatalyst for enhancing visible light response and preparation method thereof |
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| CN1412151A (en) * | 2002-12-05 | 2003-04-23 | 北京工业大学 | Ferroelectric storage material perovskite type SrBi2 Ta2O9 aramic powder and its preparation method |
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