CN112808282A - Cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, and preparation method and application thereof - Google Patents
Cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000011258 core-shell material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 92
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 92
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 92
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 92
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 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 claims abstract description 21
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 cesium-lead cation Chemical class 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- IWDXBHSUFKRAQP-UHFFFAOYSA-N [Cs].[Pb] Chemical compound [Cs].[Pb] IWDXBHSUFKRAQP-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 18
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 15
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 13
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 claims description 12
- 229940046892 lead acetate Drugs 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005265 dialkylamine group Chemical group 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical group CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 abstract description 2
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B01J35/39—
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- B01J35/397—
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- B01J35/51—
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- 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
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
Abstract
The invention discloses a cesium lead bromine perovskite crystal (CsPb)xBry0.25 ≦ x ≦ 2,1.5 ≦ y ≦ 5) @ Silica (SiO)2) The hollow mesoporous spherical core-shell structure, the preparation method and the application thereof are disclosed, wherein the method comprises the following steps: mixing SiO2Adding the hollow mesoporous spheres into a precursor organic solution containing Cs and Pb cations; the precursor solution is evacuated for a period of time (SiO2Pumping out air in the hollow mesoporous spheres, and allowing the precursor solution to enter the hollow spheres); adding a precursor solution containing bromine atoms into S2; by controlling the time andtemperature preparation of size-controllable CsPbxBry@SiO2A core-shell structure; the prepared CsPbxBry@SiO2The hollow mesoporous spheres are used for photocatalytic degradation of rhodamine B, and can be used for photocatalytic degradation of rhodamine B.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a cesium lead bromoperovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, and a preparation method and application thereof.
Background
With the rapid development of economy and the rapid rise of the quality of life of people, environmental pollution becomes increasingly serious. The serious influence of various organic matters and dye pollution on living environment of people draws wide attention. Typical organic dyes such as rhodamine B are artificially synthesized dyes and widely exist in printing and dyeing wastewater. According to research, rhodamine B is suspected of being a carcinogenic substance and is difficult to biodegrade, and the large amount of rhodamine B causes great harm to water environment. For environmental protection and human health, it is necessary to convert a substance similar to rhodamine B into a non-toxic and harmless substance. Photocatalytic degradation of such materials has become an effective method of great interest.
TiO currently in use2Photochemical catalysts have excellent photocatalytic degradation performance, but are mainly degraded by ultraviolet light, have low light utilization rate and are not suitable for large-scale application. The cesium-lead halide is a semiconductor nanoparticle, has strong absorption and high electron hole separation efficiency from ultraviolet to visible spectrum, has better photocatalytic potential in the field of photocatalysis, and has development value. However, cesium lead halides have poor stability and are difficult to exist in an aqueous environment, and thus it is difficult to apply cesium lead halides to photocatalysis of aqueous pollutants. The mesoporous hollow sphere has wide application in the field of photocatalysis, and the mesoporous structure of the mesoporous hollow sphere enables the specific surface area of the mesoporous hollow sphere to be large, so that the catalytic effect of the loaded photocatalyst is improved. Cesium-lead halide grows inside the mesoporous hollow sphere for the first time, and the water stability and the photocatalytic effect of the mesoporous hollow sphere are well realized.
Based on SiO2The cesium-coated lead halide patents are mainly CN 108531173 a (publication No. 2018.09.14) and CN 110499150 a (publication No. 2019.11.26). Respectively discloses a method for coating cesium lead bromine perovskite by silicon dioxide, which is mainly a method from inside to outside, and specifically comprises the steps of firstly forming cesium lead bromine nanocrystalline and then coating the surface of the cesium lead bromine nanocrystalline, so that cesium lead is coatedThe surface state of bromine has a great influence. We mainly go through the outside-in method, specifically synthesize SiO first2The hollow ball is used as a container, cesium lead bromine nano particles are formed in the hollow ball, the cesium lead bromine surface state is prevented from being influenced, and parameters such as the composition, the particle size and the like of the perovskite can be adjusted according to reaction conditions. The cesium-lead halide-based photocatalyst mainly comprises CN 110227532A (published Japanese 2019.09.13) and CN 111905777A (published Japanese 2020.11.10), and respectively discloses a preparation method of a cesium-lead bromide quantum dot/carbon nitride nanosheet photocatalyst and a cesium-lead bromide quantum dot composite BiWO6A photocatalyst and a preparation method thereof. The related photocatalytic material mainly realizes photocatalysis in an organic phase system.
The existing cesium-lead halide photocatalyst mainly aims at photocatalytic degradation in an organic system, and the photocatalytic treatment of organic pollutants in common waste water is rare.
Disclosure of Invention
The invention aims to provide CsPbxBry@SiO2A preparation method of a core-shell structure photocatalyst. The method has the advantages of low cost, relatively simple preparation, easy operation and feasibility and is suitable for large-batch industrial production.
The invention provides spherical CsPb synthesized by adopting an improved thermal injection technology and a coating technologyxBry@SiO2(x is more than or equal to 0.25 and less than or equal to 2, and y is more than or equal to 1.5 and less than or equal to 5) the preparation method of the mesoporous sphere with the core-shell structure has controllable size and obviously improved stability and water solubility. CsPbxBry@SiO2With the increase of the precursor proportion of the cesium-lead ions, the secondary Cs can be realized4PbBr6@SiO2, Cs4PbBr6/CsPbBr3@SiO2，CsPbBr3@SiO2，CsPb2Br5/CsPbBr3@SiO2To CsPb2Br5@SiO2And (4) converting the core-shell structure nanoparticles.
In order to achieve the purpose, the invention provides the following technical scheme:
cesium-lead-bromine-calcium-titanium alloyOre @ silicon dioxide hollow mesoporous spheres (CsPb)xBry@SiO2) A method for preparing a core-shell structure, said method comprising the steps of:
（1）SiO2preparing hollow mesoporous spheres;
(2) preparation of cesium-lead cation precursor: weighing cesium carbonate and lead acetate, adding the cesium carbonate and the lead acetate into octadecene, heating to 60-150 ℃ in a vacuum environment, and stirring for 0.5-3 h at the temperature to obtain a reactant solution; injecting the mixed solution of oleic acid and dialkyl amine into the reactant solution, and controlling the temperature of the solution at 60-150 ℃ until the reactants are completely dissolved in an inert atmosphere, wherein the molar ratio of cesium atoms to lead atoms is 1 (0.1-4); adding 1-3 mL of oleic acid and 0.5-2.5 mmol of dialkyl amine into every 0.049mmol of cesium carbonate,
(3) cesium-lead cation precursor infiltrated SiO2Preparing hollow mesoporous spheres: SiO 22Dissolving the hollow mesoporous spheres in octadecene, injecting the reactant solution in the step (2), and vacuumizing to remove SiO2Air is filled in the hollow mesoporous spheres; 10 mg-50 mg of SiO are required to be added into every 0.049mmol of cesium carbonate2A hollow ball with a hole in the middle,
(4) forming a core-shell structure of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous spheres: and (3) dissolving a bromine source in octadecene, then injecting the octadecene into the reactant solution obtained in the step (3), reacting for 5-300 s, cooling the temperature of the reactant solution to room temperature, adding a mixture of ethyl acetate and toluene into the reactant solution, centrifuging, collecting a product, and performing vacuum drying to obtain the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, wherein the molar ratio of cesium atoms to benzoyl bromide is 1 (5-20).
Preparation of SiO by improved stober method2Hollow mesoporous spheres: adding 1mL of concentrated ammonia water (25 wt%) into a mixture of 250mL of ethanol and water, adding 5.6g of CTAB, stirring and mixing uniformly, heating the mixture to 30-40 ℃, injecting 1-1.1 mL of silicon source during stirring, keeping the temperature of 30-40 ℃, stirring for 20-30 h, centrifuging to collect a white product, cleaning with ethanol, adding pure water, stirring for 30-50 h at 30-40 ℃ to grow SiO2Centrifuging, washing with ethanol, and collecting SiO2A ball;
mixing SiO2Transferring the balls into 120mL of ethanol solution containing 240 mu L of concentrated hydrochloric acid, stirring for 1-6 h at 50-70 ℃, repeating for 1-4 times, and cleaning with ethanol to remove SiO in the template2Hollow spheres; vacuum drying to obtain the final product.
Preferably, the volume ratio of the ethanol to the water is 1 (0.5-4), and the silicon source is: the bis- [ (triethoxysilyl) propyl ] -tetrasulfide and the ethyl orthosilicate are added according to the volume ratio of (0-0.5): 1. The volume ratio of the ethyl acetate to the toluene is 1 (0.25-1).
Preferably, SiO2Growing SiO in preparation of hollow mesoporous spheres2The pure water added into the ball is 200-500 mL.
Preferably, the cesium lead cation precursor permeates the SiO2In the preparation of the hollow mesoporous spheres, the mesoporous spheres are added into cesium lead cation precursors by an injection method and dissolved in ODE but not limited to ODE solution. Adding a cesium-lead cation precursor, and vacuumizing for 1-60 min at the temperature of normal temperature to 150 ℃.
The dihydrocarbylamine is didecylamine but is not limited to didecylamine and the bromine source is benzoyl bromide but is not limited to benzoyl bromide.
The cesium lead bromoperovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, CsPb, prepared by the preparation methodxBry@SiO2In the core-shell structure, the size of the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spheres is 40 nm-800 nm. SiO 22The diameter of the hollow mesoporous sphere is 40 nm-800 nm, the inner diameter of the hollow sphere is 50 nm-700 nm, and SiO is2The size of the cesium lead bromine perovskite in the hollow mesoporous sphere is 5-700 nm.
Preferably, CsPbxBry@SiO2SiO in core-shell structure photocatalyst2The cesium lead bromine perovskite in the hollow sphere is partially filled or completely filled with SiO2The hollow ball.
The application of the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere core-shell structure in degrading rhodamine B comprises the following steps: adding a cesium lead bromoperovskite and silicon dioxide hollow mesoporous spherical core-shell structure into wastewater containing rhodamine B, and illuminating by adopting a white light source of 190-1100 nm, wherein the adding amount of the cesium lead bromoperovskite and silicon dioxide hollow mesoporous spherical core-shell structure is 1-20 times of the mass of the rhodamine B.
The invention aims to provide CsPbxBry@SiO2A preparation method of hollow mesoporous sphere photocatalyst. The method has the advantages of low cost, simple raw materials, easy operation and suitability for large-batch industrial production.
The CsPb synthesized by adopting the improved thermal injection technologyxBry@SiO2The preparation method of the core-shell structure photocatalyst obviously improves the size, the stability and the water solubility.
The photocatalyst has the following advantages:
the invention discloses CsPbxBry@SiO2The core-shell structure photocatalyst has good stability in water systems and organic solvent systems such as water, dimethyl sulfoxide, ethyl acetate, toluene and the like, and is suitable for photocatalytic applications such as organic dye degradation and water photolysis based on the solvents.
The invention discloses CsPbxBry@SiO2The core-shell structure photocatalyst has excellent photoelectron absorption and conduction performance, and effectively improves the performance of photocatalytic applications such as organic dye degradation and the like.
The invention discloses CsPbxBry@SiO2The core-shell structure photocatalyst can obtain composite perovskite nanocrystalline along with the change of the cesium-lead proportion, so that a heterostructure is formed, and the performance of photocatalytic applications such as mechanical dye degradation can be effectively improved.
The invention discloses CsPbxBry@SiO2The core-shell structure photocatalyst can realize CsPb to CsPb along with the change of the loaded cesium-lead-bromine perovskitexBry@SiO2And adjusting and controlling the photocatalytic performance of the core-shell structure.
The invention discloses CsPbxBry@SiO2CsPb in core-shell structured photocatalystxBryThe particle size control of CsPb can be adjustedxBry@SiO2The performance of the photocatalyst.
The invention controls the content of cesium and leadThe cation proportion can adjust the pure phase and the composite structure of the halide perovskite, and the material can be selected from Cs4PbBr6@SiO2, Cs4PbBr6/CsPbBr3@SiO2, CsPbBr3@SiO2, CsPb2Br5/CsPbBr3@SiO2To CsPb2Br5@SiO2To be controlled. The prepared CsPbxBry@SiO2The hollow mesoporous spheres are used for photocatalytic degradation of rhodamine B, and can be used for photocatalytic degradation of rhodamine B.
Compared with the prior art, CsPb based on hollow mesoporous spheresxBry@SiO2The core-shell structure is characterized in that the core-shell structure is prepared by an outside-in method, namely SiO is prepared firstly2Hollow mesoporous spheres, and then cesium lead bromine perovskite crystals are generated in the hollow mesoporous spheres. The precursor is permeated into the hollow mesoporous sphere, and then chemical reaction and curing are carried out to form CsPbxBryPerovskite crystals. CsPb can be realized by controlling cation ratio, reaction time, temperature and the likexBryNanocrystalline in SiO2The size in the hollow sphere can be controlled to grow. CsPb obtained by the methodxBry@SiO2The hollow mesoporous sphere core-shell structure can maintain the surface structure and the surface state of the cesium-lead-bromine crystal, and has good stability and photocatalytic performance.
Drawings
FIG. 1 shows CsPbBr3@SiO2(Black curve, Cs: Pb =1: 1.6) and CsPbBr3/CsPb2Br5@SiO2(red curve, Cs: Pb =1: 2.4) X-ray diffraction pattern of core-shell structure; wherein PDF #18-0364 is CsPbBr3The standard card is CsPb with PDF #25-02112Br5A standard card;
FIG. 2 shows CsPbBr prepared in example 13@SiO2Scanning electron microscopy of core-shell structures;
FIG. 3 is CsPbBr prepared in example 33/CsPb2Br5@SiO2Scanning electron microscopy of core-shell structures;
FIG. 4 is a schematic view ofCsPbBr prepared in example 93/CsPb2Br5@SiO2Transmission electron microscopy of core-shell structures;
FIG. 5 is CsPbBr prepared in example 103/CsPb2Br5@SiO2Scanning electron microscope image of core-shell structure;
FIG. 6 shows rhodamine B in CsPbxBry@SiO2And (3) a rhodamine B concentration change graph under catalysis with different x-y ratios.
Detailed Description
The embodiments of the present invention are described below by way of specific examples, and other advantages and features of the present invention will become apparent to those skilled in the art from the description herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
In the following examples, lead acetate trihydrate (formula: C)4H6O4Pb·3H2O, purity: 99.99%), cesium carbonate (chemical formula: cs2CO3Purity: 99.9%), benzoyl bromide (formula: c6H5BrO, purity:>98%), didecylamine (formula: c20H43N, purity: 98%), oleic acid (formula: c18H34O2Purity: 90%), octadecene (formula: c18H36Purity: 90%), toluene (formula: c7H8Purity: 99%), ammonia (chemical formula: NH (NH)3·H2O, purity: AR, 25-28%), hydrochloric acid (chemical formula: HCl, purity: 36-38%), cetyltrimethylammonium bromide (CTAB) (chemical formula: c19H42BrN, purity: for molecular biology, 99%) Tetraethoxysilane (TEOS), bis- [ (triethoxysilyl) propyl]Tetrasulfide (TESPTS), rhodamine B (formula: C)28H21ClN2O3Purity: AR).
Lead acetate was trihydrate in each of the following examples.
Example 1: preparation of CsPbBr3@SiO2Core-shell structured nanoparticles
SiO2Preparing a ball: concentrated ammonia (25 wt%, 1 mL), ethanol (100 mL) and water (150 mL) (ethanol: water volume ratio of 1: 1.5) were mixed, CTAB (15 mmol, 5.6 g) was dissolved in the mixed solution and stirred (700 rpm), the mixture was heated to 35 ℃ and 1mL of ethyl orthosilicate was injected during stirring. After stirring for 24h at 35 ℃, the white product was collected by centrifugation at 4000rpm for 10min and washed three times with ethanol (15-30 mL). Adding pure water (300 mL), stirring at 35 deg.C for 40h to grow SiO2A ball. Centrifuging, washing with ethanol for three times, and collecting SiO2A ball.
SiO2Preparing hollow spheres: transferred to a solution of hydrochloric acid (240 μ L, 37 wt%) in ethanol (120 mL), stirred at 60 ℃ for 3h, and repeated twice. Cleaning with ethanol to remove SiO of template2Hollow ball for three times; vacuum drying at 40 deg.C for 3 h.
Preparing cesium and lead precursors: 0.016g of cesium carbonate (4.9X 10) is weighed using a modified hot injection technique-5mol), 0.0608g of lead acetate (1.6X 10-4mol) is added into 10mL of octadecene, and the mixture is heated to 115 ℃ in a vacuum-pumping environment (a micro air pump pumps vacuum in a triangular flask for reaction) and the temperature is maintained for 1 h; injecting a mixed solution of 1.5mL of oleic acid and 1.25mmol of didecylamine into the reactant solution, and dissolving the reactants in a nitrogen atmosphere; the temperature was reduced to 90 ℃.
10mg of hollow mesoporous SiO2The spheres were dissolved in 2mL of octadecene and then injected into the reactant solution. And then vacuumizing for 5-10 min.
Measuring 100 muL (8.5 multiplied by 10)-4mol) benzoyl bromide was dissolved in 1mL anhydrous octadecene, then injected into the reactant solution, reacted for 15s, rapidly cooled in ice bath, and the temperature of the reactant solution was reduced to room temperature. Mixing 16mL of ethyl acetate and 4mL of toluene, adding the mixture into a related solution to destroy the colloidal stability, centrifuging at 9000rpm for 10min to collect a product, repeating the process for 2-3 times, and vacuum drying at 40 ℃ for 3h to obtain CsPbBr3@SiO2Core-shellThe X-ray diffraction pattern and the scanning electron micrograph of the structured photocatalyst are shown in figures 1 and 2, and CsPbBr is shown in figure 13@SiO2(black curve, Cs: Pb =1: 1.6) X-ray diffraction pattern of core-shell structure, shown in fig. 2 as Cs: CsPbBr of Pb =1:1.63@SiO2Scanning electron micrograph shows that the obtained compound is CsPbBr3@SiO2Core-shell structure, CsPbBr3@SiO2The size is about 500nm, SiO2The diameter of the hollow mesoporous sphere is 500nm, and the inner diameter of the hollow mesoporous sphere is 400 nm.
Example 2: the result of changing the concentration of the reagent in a certain range of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is unchanged. The other steps are exactly the same as example 1, except that 0.16g of cesium carbonate (4.9X 10) is weighed in the step of preparing cesium and lead precursors-4mol), 0.608g of lead acetate (1.6X 10)-3mol) is added into 20mL of octadecene, 1mL of benzoyl bromide is measured and dissolved in 1mL of anhydrous octadecene, and CsPbBr is prepared3@SiO2Core-shell structured nanoparticles.
Example 3: the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is regulated and controlled by changing the proportion of cesium-lead cations. The other steps are all in full agreement with example 1, except that the cesium to lead molar ratio was changed to 1:2.4 (0.016 g cesium carbonate, 0.091g lead acetate were weighed) in the step of preparing cesium and lead precursors, and CsPbBr was prepared3/CsPb2Br5@SiO2The X-ray diffraction pattern and the scanning electron microscope pattern of the core-shell structure nano-particles are shown in figure 1 and figure 3. FIG. 1 shows the red curve that the compound structure is CsPbBr3/CsPb2Br5@SiO2As can be seen in FIG. 3, CsPbBr3/CsPb2Br5@SiO2Size 500nm, SiO2The diameter of the hollow mesoporous sphere is 500nm, and the hollow inner diameter is 400 nm.
Example 4: the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is regulated and controlled by changing the proportion of cesium-lead cations. The other steps are completely in accordance with example 1, the molar ratio of cesium to lead is changed to 1:2.8 only in the step of preparing cesium and lead precursors (weighing0.016g of cesium carbonate, 0.1064g of lead acetate), CsPb was prepared2Br5@SiO2Core-shell structured nanoparticles.
Example 5: the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is regulated and controlled by changing the proportion of cesium-lead cations. The other steps are completely the same as example 1, and the molar ratio of cesium to lead is changed to 1:0.2 (0.016 g of cesium carbonate and 0.0076g of lead acetate are weighed) only in the step of preparing cesium and lead precursors, so as to prepare Cs4PbBr6@SiO2Core-shell structured nanoparticles.
Example 6: the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is regulated and controlled by changing the proportion of cesium-lead cations. The other steps are completely the same as example 1, and the molar ratio of cesium to lead is changed to 1:0.8 (0.016 g of cesium carbonate and 0.0304g of lead acetate are weighed) only in the step of preparing cesium and lead precursors, so as to prepare Cs4PbBr6/CsPbBr3@SiO2Core-shell structured nanoparticles.
In conclusion, Cs obtained when the molar ratio of cesium to lead is 1 (0.1-0.4)4PbBr6@SiO2The core-shell structure nano particle has a cesium-lead molar ratio of 1 (0.1-0.4) (excluding 1: 0.4) and is obtained by (1) (0.4-1.3) (excluding 1: 1.3) being Cs4PbBr6/CsPbBr3@SiO2The core-shell structure nano particle has a cesium-lead molar ratio of 1 (1.3-1.6) and CsPbBr3@SiO2The core-shell structure nano particle has a cesium-lead molar ratio of 1 (1.6-2.8) (excluding two endpoint values of 1:1.6 and 1: 2.8) and is CsPbBr3/CsPb2Br5@SiO2The nano particle with a core-shell structure has a cesium-lead molar ratio of more than 1:2.8 and is CsPb2Br5@SiO2Core-shell structured nanoparticles.
Example 7: the reaction temperature of cesium-lead cations and benzoyl bromide is changed for a cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst. The other steps are completely consistent with those of the example 6, and only the mixed solution of the dialkyl amine is injected into the reactant solution until the reactants are completely dissolved in the nitrogen atmosphere; temperature ofThe temperature is controlled to be 60-150 ℃, and Cs is prepared4PbBr6/CsPbBr3@SiO2Core-shell structured nanoparticles.
Example 8: the reaction time of cesium-lead cations and benzoyl bromide is changed for a cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst. The other steps are completely consistent with those in the embodiment 6, the benzoyl bromide is only dissolved in 1mL of anhydrous octadecene and then injected into the reactant solution, the reaction time is controlled to be 5 s-300 s, and the Cs is prepared4PbBr6/CsPbBr3@SiO2Core-shell structured nanoparticles.
Example 9: SiO of cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is changed2Changing the silicon source in the preparation of the ball to SiO2And (5) adjusting the sphere diameter. The other steps are all identical to those in example 3, only in SiO2During the preparation of the ball, changing l mL TEOS into 0.3mL TESPTS and 0.75mL TEOS to obtain SiO2The sphere diameter was about 100nm (shown in FIG. 4). FIG. 4 shows that CsPbBr3/CsPb2Br5@SiO2The size of the film is about 100nm and SiO2The diameter of the hollow mesoporous sphere is about 100nm, and the inner diameter of the hollow mesoporous sphere is about 50 nm.
Example 10: SiO of cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere photocatalyst is changed2SiO is carried out according to the proportion of water and ethanol in the preparation process of the ball2And (5) adjusting the sphere diameter. The other steps are all identical to those in example 3, only in SiO2In the preparation process of the ball, the volume ratio of water to ethanol is 1 (0.3-3), and SiO shown in figure 52(sphere diameter about 400 nm) the volume ratio of water to ethanol in the preparation process was 1:0.8, and the total volume of water and ethanol was still 250 mL. FIG. 5 shows that CsPbBr3/CsPb2Br5@SiO2Size of about 400nm, SiO2The diameter of the hollow mesoporous sphere is about 400nm, and the hollow inner diameter is about 310 nm.
Application experiments
100mL of rhodamine B solution with the concentration of 20mg/L is prepared, poured into a transparent container with cooling water circulation, and then cesium lead bromoperovskite nanocrystalline @ SiO is added2Core-shell structure nano particle powder 40mg, and using tin foil paperThe cup mouth (the inner diameter of the round cup: 4.5 cm) is sealed to shield the light. Stirring for 30min, collecting 2mL solution, turning on white light source (xenon lamp, wavelength range: 190-1100 nm, illumination intensity: 2.8 mW), illuminating the solution from top to bottom with the lamp 4cm away from the cup mouth, and carrying out photoreaction. 2mL of the solution was taken every 20min, and 8 times of the solution were taken. Followed by centrifugation at 12000rpm for 5min, repeated once. The concentration of the solution taken out is obviously changed, wherein when the ratio of cesium to lead is 1:2.4, the degradation effect on rhodamine is best, the degradation rate on rhodamine B after 20min reaches 60%, and after 160min, the concentration of rhodamine B is reduced from 20mg/L to about 3mg/L, and the degradation rate is 87%.
The foregoing detailed description has been presented by way of example for purposes of clarity of understanding the patent and is not to be construed as limiting the scope of the patent; all equivalent changes and modifications made according to this patent are intended to be covered by this patent.
Claims (9)
1. A preparation method of a cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous sphere core-shell structure is characterized by comprising the following steps:
（1）SiO2preparing hollow mesoporous spheres;
(2) preparation of cesium-lead cation precursor: weighing cesium carbonate and lead acetate, adding the cesium carbonate and the lead acetate into octadecene, heating to 60-150 ℃ in a vacuum environment, and stirring for 0.5-13 h at the temperature to obtain a reactant solution; injecting the mixed solution of oleic acid and dialkyl amine into the reactant solution, and controlling the temperature of the solution at 60-150 ℃ until the reactants are completely dissolved in an inert atmosphere, wherein the molar ratio of cesium atoms to lead atoms is 1 (0.1-4); adding 1-3 mL of oleic acid and 0.5-2.5 mmol of dialkyl amine into every 0.049mmol of cesium carbonate,
(3) cesium-lead cation precursor infiltrated SiO2Preparing hollow mesoporous spheres: SiO 22Dissolving the hollow mesoporous spheres in octadecene, injecting the reactant solution in the step (2), and vacuumizing to remove SiO2Air is filled in the hollow mesoporous spheres; 10 mg-50 mg of SiO are required to be added into every 0.049mmol of cesium carbonate2A hollow ball with a hole in the middle,
(4) forming a core-shell structure of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous spheres: and (3) dissolving a bromine source in octadecene, then injecting the octadecene into the reactant solution obtained in the step (3), reacting for 5-300 s, cooling the temperature of the reactant solution to room temperature, adding a mixture of ethyl acetate and toluene into the reactant solution, centrifuging, collecting a product, and performing vacuum drying to obtain the cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, wherein the molar ratio of cesium atoms to benzoyl bromide is 1 (5-20).
2. The preparation method of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous sphere core-shell structure according to claim 1, characterized in that SiO2The preparation process of the hollow mesoporous spheres is as follows:
adding concentrated ammonia water into a mixture of ethanol and water, adding CTAB, stirring and mixing uniformly, heating the mixture to 30-40 ℃, injecting a silicon source during stirring, keeping the temperature at 30-40 ℃, stirring for 20-30 h, centrifuging to collect a white product, cleaning with ethanol, adding pure water, stirring for 30-50 h at 30-40 ℃ to grow SiO2Centrifuging, washing with ethanol, and collecting SiO2The ball, the proportion of strong ammonia water, CTAB, silicon source is: 1mL of: 5.6 g: (1-1.1) mL;
mixing SiO2Transferring the balls into an ethanol solution containing concentrated hydrochloric acid, stirring for 1-6 h at 50-70 ℃, repeating for 1-4 times, and cleaning with ethanol to remove SiO in the template2Hollow spheres; vacuum drying to obtain the final product.
3. The preparation method of the cesium lead bromine perovskite @ silicon dioxide hollow mesoporous sphere core-shell structure according to claim 2, wherein 250mL of a mixture of ethanol and water is required to be added to every 1mL of concentrated ammonia water, and the volume ratio of the ethanol to the water is 1 (0.5-4).
4. The preparation method of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous sphere core-shell structure according to claim 2, wherein a silicon source is bis- [ (triethoxysilyl) propyl ] -tetrasulfide and tetraethoxysilane added in a volume ratio of (0-0.5): 1.
5. The preparation method of the cesium lead bromoperovskite @ silicon dioxide hollow mesoporous sphere core-shell structure according to claim 1, wherein the volume ratio of ethyl acetate to toluene is 1 (0.25-1).
6. The method for preparing a cesium lead bromoperovskite @ silica hollow mesoporous sphere core-shell structure according to claim 1, wherein the dialkyl amine is didecyl amine but not limited to didecyl amine, and the bromine source is benzoyl bromide but not limited to benzoyl bromide.
7. The cesium lead bromine perovskite @ silica hollow mesoporous spherical core-shell structure prepared by the preparation method as claimed in any one of claims 1 to 6.
8. The application of the cesium lead bromoperovskite @ silica hollow mesoporous sphere core-shell structure as defined in claim 7 in degrading rhodamine B.
9. Use according to claim 8, characterized in that the procedure is as follows: adding a cesium lead bromoperovskite and silicon dioxide hollow mesoporous spherical core-shell structure into wastewater containing rhodamine B, and illuminating by adopting a white light source of 190-1100 nm, wherein the adding amount of the cesium lead bromoperovskite and silicon dioxide hollow mesoporous spherical core-shell structure is 1-20 times of the mass of the rhodamine B.
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