CN113976174A - Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework - Google Patents
Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework Download PDFInfo
- Publication number
- CN113976174A CN113976174A CN202111194624.8A CN202111194624A CN113976174A CN 113976174 A CN113976174 A CN 113976174A CN 202111194624 A CN202111194624 A CN 202111194624A CN 113976174 A CN113976174 A CN 113976174A
- Authority
- CN
- China
- Prior art keywords
- mil
- pbx
- organic
- inorganic perovskite
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 17
- -1 methyl amine halide Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 18
- 239000006228 supernatant Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 4
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012917 MOF crystal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SLFLFNSLWZNOOG-UHFFFAOYSA-N ethanol;hydroiodide Chemical compound [I-].CC[OH2+] SLFLFNSLWZNOOG-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/39—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Abstract
The invention discloses a preparation method of a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material. The preparation method comprises the following steps: mixing PbX2Dissolving (X ═ Br, I) powder in DMF, adding to MIL-101(Cr) powder, and stirring at room temperature to obtain PbX2@ MIL-101 (Cr); the obtained PbX is subjected to2Mixing @ MIL-101(Cr) with methyl amine halide (MAX, X ═ Br, I) ethanol solution, stirring at room temperature to obtain MAPbX3@ MIL-101(Cr) composite material. Compared with pure organic and inorganic perovskite, the stability is greatly improved, and simultaneously, due to the introduction of MOFs materials, the pore structure of the materials is enriched. The composite material shows higher catalytic performance in the preparation of carbon monoxide and methane by photocatalytic carbon dioxide reduction, and has good application prospect.
Description
Technical Field
The invention relates to the field of metal organic framework material derivatives, in particular to a preparation method of a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material.
Background
The organic-inorganic perovskite has the advantages of high cost benefit, adjustable emission, high photoluminescence quantum yield, excellent carrier property and the like, and has good photoelectric and photovoltaic application prospects. However, the potential applications of the entire organic-inorganic perovskite material are facing a significant challenge, because it is less resistant to moisture, polar solvents, temperature and light, which limits the applications of such organic-inorganic perovskite materials in the field of catalysis to some extent. One possible strategy to improve the stability of organic-inorganic perovskites is to incorporate them into porous templates.
The metal organic framework material (abbreviated as MOFs material) is a porous functional material which is rapidly and continuously developed in recent years, and is a zeolite-like material which is formed by self-assembling metal ions or metal clusters and organic ligands through coordination bonds and has a micropore network structure. MOFs have excellent properties, ultra-high specific surface, regular pore structure, controllable pore size and surface chemical group modification, and unique ordered/functional pore networks, which make them promising as such porous templates. The method can accommodate wide organic and inorganic perovskite in a nano area, simultaneously minimize particle aggregation, improve the stability of captured substances, and have wide application prospect in the field of catalysis.
Therefore, the method for simply preparing the organic-inorganic perovskite @ MOFs composite material at room temperature is a challenge for material research workers, and is a higher requirement for social development demands in the field of MOFs materials.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material. The invention uses PbX2MAX is a precursor, is introduced into an MIL-101(Cr) pore channel in two steps, and forms organic and inorganic perovskite MAPbX in the pore channel by an in-situ growth method3。
The purpose of the invention is realized by at least one of the following technical solutions.
A preparation method of a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material comprises the following steps:
(1) mixing PbX2Dissolving the powder in DMF, and ultrasonically dispersing and dissolving to obtain PbX2A perovskite precursor solution;
(2) the PbX obtained in the step (1) is treated2Adding the perovskite precursor solution into MIL-101(Cr) powder, performing ultrasonic dispersion, and stirring at normal temperature to obtain PbX2@ MIL-101(Cr) suspension, further centrifuged, washed and dried to obtain PbX2@ MIL-101(Cr) material;
(3) dissolving MAX powder in an ethanol solution, and performing ultrasonic dispersion and dissolution to obtain a MAX perovskite precursor solution; PbX obtained in the step (2)2@ MIL-101(Cr) in a toluene solution;
(4) quickly adding the MAX perovskite precursor solution obtained in the step (3) into the PbX obtained in the step (3)2The method comprises the steps of stirring at room temperature, centrifuging, washing and drying in a toluene solution of @ MIL-101(Cr) to obtain MAPbX3@ MIL-101(Cr) composite material.
Further, in the step (1), PbX2The concentration of the perovskite precursor solution is 0.055-0.14 mol/L; in the step (3), the concentration of the MAX perovskite precursor solution is 0.055-0.14 mol/L.
Further, PbX2And in MAX, X is Br or I.
Further, in the step (2), the stirring time at normal temperature is 6-72 h, the centrifugation condition is 8000-10000 r/min, the centrifugation time is 10-15 min, the drying time is 6-24 h, and the drying temperature is 50-70 ℃.
Further, in the step (2), the washing condition is one time of washing with a DMF solution.
Further, in the step (2), the method for preparing MIL-101(Cr) powder comprises the following steps:
1) mixing Cr (NO)3)3·9H2Adding O, terephthalic acid, hydrofluoric acid and deionized water into the inner liner of the reaction kettle, ultrasonically dispersing, placing in a 200-220 ℃ oven, keeping the temperature for 7-8 h, and slowly cooling to room temperature for 12-15 h;
2) filtering the solution obtained in the step 1) by using a G2 funnel, pouring the obtained green filtrate into a G4 funnel, respectively washing the green filtrate by using deionized water and ethanol for 5-10 times, dispersing the green filtrate into a 95% ethanol solution, putting the solution into a reaction kettle, and standing the reaction kettle in an oven at 70-80 ℃ for 24-30 hours;
3) filtering while hot to obtain MIL-101(Cr) green powder, and finally vacuum-drying the obtained green powder at 150-200 ℃ for 10-12 h, and activating for later use.
Further, in the step (3), PbX is dispersed2The volume of the toluene solution of @ MIL-101(Cr) material was 1 mL.
Further, in the step (4), the stirring condition is that the stirring time is 5-15 min, and the stirring speed is 400-900 r/min.
Further, the centrifugation condition in the step (4) is 5000-10000 r/min, and the centrifugation time is 3-10 min.
Further, in the step (4), the washing condition is that a cyclohexane solution is used for washing once, the drying time is 6-24 hours, and the drying temperature is 70 ℃.
The invention provides a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the invention has simple operation and comprises two synthesis steps, PbX2The @ MIL-101(Cr) precursor material can be obtained by stirring for several hours at normal temperature; and MAPbX3The @ MIL-101(Cr) composite material can be obtained by stirring at room temperature in one step;
(2) the synthesis method can be completed under the conditions of room temperature and stirring, a high-temperature reaction kettle and inert gas protection are not needed for reaction, the operation is simple, and the conditions required by synthesis and the professional technical requirements of experimental operators are greatly reduced;
(3) the synthesis method of the invention utilizes the high specific surface and porosity of MIL-101(Cr) to nucleate and grow the organic-inorganic perovskite in the pores of MIL-101(Cr) by an in-situ growth method, thereby overcoming the problem that the organic-inorganic perovskite is difficult to enter the MOF crystal pores due to the large pores of the MOF crystal;
(4) MAPbX prepared by the invention3The @ MIL-101(Cr) composite material improves the stability of the organic-inorganic perovskite and simultaneously enhances the photocatalytic performance of the organic-inorganic perovskite.
Drawings
FIG. 1 is a PXRD curve for MIL-101(Cr) material obtained in example 1;
FIG. 2 is an SEM picture of the MIL-101(Cr) material obtained in example 1;
FIG. 3 shows MAPbBr obtained in example 23SEM picture of @ MIL-101(Cr) composite material;
FIG. 4 shows MAPbBr obtained in example 23TEM pictures of @ MIL-101(Cr) composite;
FIG. 5 shows MAPbBr obtained in examples 2, 3, 4 and 53The PXRD curve for @ MIL-101(Cr) composite material;
FIG. 6 shows the MAPbI obtained in example 63TEM pictures of @ MIL-101 (Cr);
FIG. 7 shows MAPbBr obtained in examples 2, 3, 4 and 53The @ MIL-101(Cr) composite material is used for preparing a performance test chart of carbon monoxide and methane by photocatalytic carbon dioxide reduction.
Detailed Description
In the following description, technical solutions are set forth in conjunction with specific figures in order to provide a thorough understanding of the present invention. This application is capable of embodiments in many different forms than those described herein and it is intended that all such modifications that would occur to one skilled in the art are deemed to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a metal organic framework material MIL-101(Cr), which comprises the following steps:
(1) mixing Cr (NO)3)3·9H2O (2g,5mmol), terephthalic acid (0.823g,5mmol), hydrofluoric acid (40 wt%, 5mmol, 250 μ L) and deionized water (24mL) are added into the inner liner of the reaction kettle, ultrasonic treatment is carried out for 30min, the mixture is placed in an oven, the temperature is heated to 220 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 8h, the temperature is reduced to 150 ℃ after 1h, and then the temperature is slowly reduced to room temperature after 12 h.
(2) Filtering the solution obtained in the step (1) by using a G2 funnel to remove unreacted terephthalic acid crystals in the solution, filtering the obtained green filtrate by using a G4 funnel to obtain green powder, respectively washing the green powder by using deionized water and 95% ethanol solution for 6 times, then dispersing the green powder in 20mL of 95% ethanol solution, putting the solution into a reaction kettle, and placing the reaction kettle in an oven at 80 ℃ for standing for 24 hours.
(3) Filtering the solution obtained in the step (2) by using a G4 funnel while the solution is hot to obtain MIL-101(Cr) powder. And finally, drying MIL-101(Cr) powder for 12 hours in vacuum at the temperature of 150 ℃, and activating for later use.
FIG. 1 shows a PXRD spectrum of MIL-101(Cr) obtained in this example. As can be seen from the figure, MIL-101(Cr) has good crystallinity and strong crystal diffraction intensity for X-rays. The PXRD characteristic diffraction peak of MIL-101(Cr) basically corresponds to the diffraction peak of MIL-101(Cr) simullate, and the green powder is the MIL-101(Cr) material.
FIG. 2 is an SEM picture obtained in this example, from which the octahedral micro-morphology of the MIL-101(Cr) material can be observed, and the surface is smooth.
Example 2
This example provides a metal organic framework encapsulated organic-inorganic perovskite (MAPbBr)3) The preparation method of the composite photocatalytic material comprises the following steps:
(1) 0.051g of PbBr2Dissolved in 1000. mu.L of DMF, added to the activated 0.1g of MIL-101(Cr) green powder obtained in example 1, and then stirred at room temperature for 72 hours. Centrifuging the obtained solution at 10000r/min for 10min at high speed, removing supernatant, washing with DMF once, and centrifuging under the same conditions to obtain green solid PbBr2@ MIL-101 (Cr). The resulting solid was placed in an oven at 70 ℃ for 12h to give a dry green powder.
(2) Dissolving 0.0157g of methyl ammonium bromide in 1000 mu L of ethanol by normal temperature ultrasonic waves, and adding PbBr obtained in the step (1)2@ MIL-101(Cr) is dispersed in 1000 microliter toluene, and the methyl ammonium bromide ethanol solution is injected into PbBr rapidly under the condition of normal temperature2@ MIL-101(Cr) in toluene, and stirred at room temperature for 10 min. Make MAPbBr3The perovskite precursor generates MAPbBr in the MIL-101(Cr) pore channel3Perovskite. Centrifuging the obtained solution at 8000r/min for 5min at high speed, removing supernatant, washing with cyclohexane once, obtaining green solid under the same centrifugation condition, placing the obtained solid in an oven at 70 ℃ for 6-24 h to obtain dry green powder MAPbBr3@ MIL-101(Cr) composite material.
FIG. 3 shows MAPbBr obtained in this example3SEM image of @ MIL-101 (Cr). As can be seen from the figure, MIL-101(Cr) encapsulates MAPbBr3And then, the micro morphology is not changed, the regular octahedral micro morphology is still maintained, and the surface is smooth.
FIG. 4 shows MAPbBr obtained in this example3TEM pictures of @ MIL-101 (Cr). As can be seen in the figure, MAPbBr3The @ MIL-101(Cr) composite material is uniformly distributed with 1-2 nm small white dots, and the MAPbBr is proved3Packaging into the pore canal of MIL-101 (Cr).
FIG. 7 shows MAPbBr obtained in examples 2, 3, 4 and 53Graph of photocatalytic performance for @ MIL-101(Cr) composite material. As can be seen in the figure, MAPbBr3The @ MIL-101(Cr) composite material has the performance superior to that of preparing carbon monoxide and methane by photocatalytic carbon dioxide reduction of pure perovskite.
Example 3
This example provides a metal organic framework encapsulated organic-inorganic perovskite (MAPbBr)3) The preparation method of the composite photocatalytic material comprises the following steps:
(1) 0.04g of PbBr2Dissolved in 1000. mu.L of DMF, added to the activated 0.1g of MIL-101(Cr) green powder obtained in example 1, and then stirred at room temperature for 72 hours. Centrifuging the obtained solution at 10000r/min for 10min at high speed, removing supernatant, washing with DMF once, and centrifuging under the same conditions to obtain green solid PbBr2@ MIL-101 (Cr). The resulting solid was placed in an oven at 70 ℃ for 12h to give a dry green powder.
(2) Dissolving 0.0123g of methyl ammonium bromide in 1000 mu L of ethanol at normal temperature by ultrasonic waves, and dissolving PbBr obtained in the step (1)2@ MIL-101(Cr) is dispersed in 1000 microliter toluene, and the methyl ammonium bromide ethanol solution is injected into PbBr rapidly under the condition of normal temperature2@ MIL-101(Cr) toluene solutionThe solution was stirred at room temperature for 10 min. Make MAPbBr3The perovskite precursor generates MAPbBr in the MIL-101(Cr) pore channel3Perovskite. Centrifuging the obtained solution at 8000r/min for 5min at high speed, removing supernatant, washing with cyclohexane once, obtaining green solid under the same centrifugation condition, placing the obtained solid in an oven at 70 ℃ for 6-24 h to obtain dry green powder MAPbBr3@ MIL-101(Cr) composite material.
Example 4
This example provides a metal organic framework encapsulated organic-inorganic perovskite (MAPbBr)3) The preparation method of the composite photocatalytic material comprises the following steps:
(1) 0.03g of PbBr was added2Dissolved in 1000. mu.L of DMF, added to the activated 0.1g of MIL-101(Cr) green powder obtained in example 1, and then stirred at room temperature for 72 hours. Centrifuging the obtained solution at 10000r/min for 10min at high speed, removing supernatant, washing with DMF once, and centrifuging under the same conditions to obtain green solid PbBr2@ MIL-101 (Cr). The resulting solid was placed in an oven at 70 ℃ for 12h to give a dry green powder.
(2) Dissolving 0.0090g of methyl ammonium bromide in 1000 mu L of ethanol at normal temperature by ultrasonic waves, and adding PbBr obtained in the step (1)2@ MIL-101(Cr) is dispersed in 1000 microliter toluene, and the methyl ammonium bromide ethanol solution is injected into PbBr rapidly under the condition of normal temperature2@ MIL-101(Cr) in toluene, and stirred at room temperature for 10 min. Make MAPbBr3The perovskite precursor generates MAPbBr in the MIL-101(Cr) pore channel3Perovskite. Centrifuging the obtained solution at 8000r/min for 5min at high speed, removing supernatant, washing with cyclohexane once to obtain green solid under the same centrifugation condition, placing the obtained solid in 70 deg.C oven for 12h to obtain dry green powder MAPbBr3@ MIL-101(Cr) composite material.
Example 5
This example provides a metal organic framework encapsulated organic-inorganic perovskite (MAPbBr)3) The preparation method of the composite photocatalytic material comprises the following steps:
1) 0.02g of PbBr was added2Dissolved in 1000. mu.L of LDMF, 0.1g of the activated MIL-101 obtained in example 1 was added(Cr) into the green powder, and then stirred at room temperature for 72 hours. Centrifuging the obtained solution at 10000r/min for 10min at high speed, removing supernatant, washing with DMF once, and centrifuging under the same conditions to obtain green solid PbBr2@ MIL-101 (Cr). The resulting solid was placed in an oven at 70 ℃ for 12h to give a dry green powder.
(2) Dissolving 0.0062g of methyl ammonium bromide in 1000 mu L of ethanol at normal temperature by ultrasonic waves, and adding PbBr obtained in the step (1)2@ MIL-101(Cr) is dispersed in 1000 microliter toluene, and the methyl ammonium bromide ethanol solution is injected into PbBr rapidly under the condition of normal temperature2@ MIL-101(Cr) in toluene, and stirred at room temperature for 10 min. Make MAPbBr3The perovskite precursor generates MAPbBr in the MIL-101(Cr) pore channel3Perovskite. Centrifuging the obtained solution at 8000r/min for 5min at high speed, removing supernatant, washing with cyclohexane once to obtain green solid under the same centrifugation condition, placing the obtained solid in 70 deg.C oven for 12h to obtain dry green powder MAPbBr3@ MIL-101(Cr) composite material.
FIG. 5 shows MAPbBr obtained from examples 2, 3, 4 and 53The PXRD pattern of @ MIL-101(Cr) from which it can be seen, in addition to the characteristic diffraction peaks of MIL-101(Cr), most notably, 2 θ ═ 15 °, 30.1 °, 33.7 ° and 43.08 ° in the PXRD pattern of the composite material correspond to pure MAPbBr3The (110), (200), (210) and (220) planes of (1). Demonstration of MAPbBr3Formation of @ MIL-101(Cr) composite material.
Example 6
This example provides a metal organic framework encapsulated organic-inorganic perovskite (MAPbI)3) The preparation method of the composite photocatalytic material comprises the following steps:
(1) 0.05g of PbI2Dissolved in 1000. mu.L of DMF, added to the activated 0.1g of MIL-101(Cr) green powder obtained in example 1, and then stirred at room temperature for 72 hours. Centrifuging the obtained solution at 10000r/min for 10min at high speed, removing supernatant, washing with DMF once, and centrifuging under the same conditions to obtain green solid PbI2@ MIL-101 (Cr). The resulting solid was placed in an oven at 70 ℃ for 12h to give a dry green powder.
(2) 0.0157g of methyliodide is addedDissolving the PbI obtained in the step (1) in 1000 mu L ethanol by warm ultrasound, and adding the PbI2@ MIL-101(Cr) is dispersed in 1000. mu.L toluene, and the methyl amine iodide ethanol solution is rapidly injected into PbI under the condition of normal temperature2@ MIL-101(Cr) in toluene, and stirred at room temperature for 10 min. Make MAPbI3The perovskite precursor generates MAPbI in an MIL-101(Cr) pore channel3Perovskite. The resulting solution was dried under vacuum at 100 ℃ to give MAPbI as a dry green powder3@ MIL-101(Cr) composite material.
FIG. 6 shows the MAPbI obtained in the present example3TEM pictures of @ MIL-101 (Cr). As can be seen from the figure, MIL-101(Cr) encapsulates MAPbI3And then, the micro morphology is not changed, the regular octahedral micro morphology is still maintained, and the surface is smooth.
It should be understood that although the terms first, second, etc. may be used herein to describe various information in one or more embodiments of the specification, these information should not be limited by these terms, which are used only for distinguishing between similar items and not necessarily for describing a sequential or chronological order of the features described in one or more embodiments of the specification. Furthermore, the terms "having," "including," and similar referents, are intended to cover a non-exclusive scope, such that a process, method, system, article, or apparatus that comprises a list of steps or modules is not necessarily limited to the particular details set forth, but may include other inherent information not expressly listed for such steps or modules.
Claims (10)
1. A preparation method of a metal organic framework packaged organic-inorganic perovskite composite photocatalytic material is characterized by comprising the following steps:
(1) mixing PbX2Dissolving the powder in DMF, and ultrasonically dispersing and dissolving to obtain PbX2A perovskite precursor solution;
(2) the PbX obtained in the step (1) is treated2Adding the perovskite precursor solution into MIL-101(Cr) powder, performing ultrasonic dispersion, and stirring at normal temperature to obtain PbX2@ MIL-101(Cr) suspension; further centrifuging, washing and drying to obtain PbX2@ MIL-101(Cr) material;
(3) dissolving methyl amine halide powder in an ethanol solution, and performing ultrasonic dispersion and dissolution to obtain MAX perovskite precursor solution; in addition, PbX obtained in the step (2) is used2@ MIL-101(Cr) in a toluene solution;
(4) adding the MAX perovskite precursor solution obtained in the step (3) into the PbX obtained in the step (3)2@ MIL-101(Cr) in toluene, stirring at room temperature, centrifuging, washing, and drying to obtain MAPbX3@ MIL-101(Cr) composite material.
2. The method for preparing the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (1), PbX is added2The concentration of the perovskite precursor solution is 0.055-0.14 mol/L; in the step (3), the concentration of the MAX perovskite precursor solution is 0.055-0.14 mol/L.
3. The method for preparing the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein PbX is added2And in MAX, X is Br or I.
4. The preparation method of the metal organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (2), the stirring time at normal temperature is 6-72 h, the centrifugation condition is 8000-10000 r/min, the centrifugation time is 10-15 min, the drying time is 6-24 h, and the drying temperature is 50-70 ℃.
5. The method for preparing the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (2), the washing condition is one washing with DMF solution.
6. The preparation method of the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (2), the preparation method of the MIL-101(Cr) powder comprises the following steps:
1) mixing Cr (NO)3)3·9H2Adding O, terephthalic acid, hydrofluoric acid and deionized water into the inner liner of the reaction kettle, ultrasonically dispersing, placing in a 200-220 ℃ oven, keeping the temperature for 7-8 h, and slowly cooling to room temperature for 12-15 h;
2) filtering the solution obtained in the step 1) by using a funnel to obtain green powder, washing the green powder by using deionized water and ethanol for multiple times, dispersing the green powder in 95% ethanol solution, putting the solution into a reaction kettle, and standing the reaction kettle in an oven at 70-80 ℃ for 24-30 hours;
3) filtering while hot to obtain MIL-101(Cr) green powder, and finally vacuum-drying the obtained green powder at 150-200 ℃ for 10-12 h, and activating for later use.
7. The method for preparing the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (3), PbX is dispersed2The volume of the toluene solution of @ MIL-101(Cr) material was 1 mL.
8. The preparation method of the metal organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (4), the stirring condition is that the stirring time is 5-15 min, and the stirring speed is 400-900 r/min.
9. The preparation method of the metal organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein the centrifugation conditions in the step (4) are 5000-10000 r/min and 3-10 min.
10. The method for preparing the metal-organic framework encapsulated organic-inorganic perovskite composite photocatalytic material as claimed in claim 1, wherein in the step (4), the washing condition is that the washing is performed once by using a cyclohexane solution, the drying time is 6-24 h, and the drying temperature is 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111194624.8A CN113976174A (en) | 2021-10-13 | 2021-10-13 | Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111194624.8A CN113976174A (en) | 2021-10-13 | 2021-10-13 | Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113976174A true CN113976174A (en) | 2022-01-28 |
Family
ID=79738530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111194624.8A Pending CN113976174A (en) | 2021-10-13 | 2021-10-13 | Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113976174A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115870009A (en) * | 2022-12-19 | 2023-03-31 | 西安科技大学 | Preparation method and application of double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs (volatile organic compounds) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634986A (en) * | 2016-11-09 | 2017-05-10 | 南京理工大学 | Metal and organic frame complex method capable of improving stability of perovskite |
| WO2019041505A1 (en) * | 2017-09-01 | 2019-03-07 | 李良 | Fluorescent perovskite nanocrystal and confidential information security application thereof |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN110449187A (en) * | 2019-07-25 | 2019-11-15 | 中山大学 | A kind of preparation method and application of perovskite-metal complex composite material |
| CN111662705A (en) * | 2020-05-21 | 2020-09-15 | 南京邮电大学 | Method for improving stability of perovskite |
| CN112619709A (en) * | 2021-03-05 | 2021-04-09 | 北京思践通科技发展有限公司 | Photocatalytic nano material and preparation method thereof |
| CN113134392A (en) * | 2021-04-26 | 2021-07-20 | 北京师范大学 | perovskite-MOFs composite photocatalyst and preparation method and application thereof |
| CN113201339A (en) * | 2021-04-09 | 2021-08-03 | 广东工业大学 | Perovskite quantum dot and metal organic framework composite luminescent material and preparation method and application thereof |
-
2021
- 2021-10-13 CN CN202111194624.8A patent/CN113976174A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634986A (en) * | 2016-11-09 | 2017-05-10 | 南京理工大学 | Metal and organic frame complex method capable of improving stability of perovskite |
| WO2019041505A1 (en) * | 2017-09-01 | 2019-03-07 | 李良 | Fluorescent perovskite nanocrystal and confidential information security application thereof |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN110449187A (en) * | 2019-07-25 | 2019-11-15 | 中山大学 | A kind of preparation method and application of perovskite-metal complex composite material |
| CN111662705A (en) * | 2020-05-21 | 2020-09-15 | 南京邮电大学 | Method for improving stability of perovskite |
| CN112619709A (en) * | 2021-03-05 | 2021-04-09 | 北京思践通科技发展有限公司 | Photocatalytic nano material and preparation method thereof |
| CN113201339A (en) * | 2021-04-09 | 2021-08-03 | 广东工业大学 | Perovskite quantum dot and metal organic framework composite luminescent material and preparation method and application thereof |
| CN113134392A (en) * | 2021-04-26 | 2021-07-20 | 北京师范大学 | perovskite-MOFs composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JI-HYUN CHA ET AL.: ""Formation and Encapsulation of All-Inorganic Lead Halide Perovskites at Room Temperature in Metal−Organic Frameworks"" * |
| JI-HYUN CHA ET AL.: ""Formation and Encapsulation of All-Inorganic Lead Halide Perovskites at Room Temperature in Metal−Organic Frameworks"", 《THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115870009A (en) * | 2022-12-19 | 2023-03-31 | 西安科技大学 | Preparation method and application of double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs (volatile organic compounds) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105817255B (en) | A kind of manganese series oxides/graphite phase carbon nitride composite photocatalyst material and preparation method thereof | |
| CN109956463A (en) | A kind of carbon nanotube and preparation method thereof | |
| CN108855220B (en) | Titanium dioxide doped ZIF and preparation method and application thereof | |
| CN108339567B (en) | Method for preparing hydrophobic zeolite catalytic material for encapsulating titanium dioxide | |
| CN108927188B (en) | Bismuth oxycarbonate photocatalyst and preparation method thereof | |
| CN113908872A (en) | Double-vacancy graphite-phase carbon nitride photocatalyst and preparation method thereof | |
| CN112442186B (en) | Metal organic framework Mn-MOF single crystal material and nanosheet as well as preparation and application thereof | |
| CN113976174A (en) | Preparation method of organic-inorganic perovskite composite photocatalytic material packaged by metal organic framework | |
| CN111013659A (en) | Graphene-doped cobalt-based metal organic framework composite material, and preparation method and application thereof | |
| CN110818911A (en) | Synthesis method of ZIF-67-Co nano material with cuboctahedral hollow structure | |
| CN108031483B (en) | Carbon-coated nitrogen-doped TiO2Synthesizing method of butterfly-shaped nano material | |
| CN114014334A (en) | Medium silicon-aluminum ratio ZSM-5 heterozygous nanosheet molecular sieve and preparation method thereof | |
| CN105170185A (en) | ZIF-8@MCM-41 molecular sieve and preparation method thereof | |
| CN114832863A (en) | Hierarchical porous metal organic framework material and preparation method and application thereof | |
| CN113019396A (en) | Preparation method and application of core-shell structured indium cadmium sulfide @ N-titanium dioxide composite photocatalyst | |
| CN108273533B (en) | Porous g-C with high specific surface area3N4Preparation method of (1) | |
| CN113354830B (en) | Synthesis method and application of uniform-size ZIF-8 metal organic framework material | |
| CN110655103A (en) | Porous CuO/In2O3Dodecahedral complex and method for preparing same | |
| CN113797965B (en) | Preparation method of titanium-silicon molecular sieve crystal-loaded copper nanoparticle catalyst | |
| CN106517227A (en) | Microwave method for rapidly preparing short-rod-like SBA-15 | |
| CN109880112B (en) | In-situ oriented arrangement one-dimensional structure ZIF-67 and preparation method thereof | |
| CN113289501A (en) | Preparation method of nano porous carbon ceramic membrane nanofiltration composite membrane | |
| CN114260027A (en) | Method for preparing metal oxide @ metal organic framework core-shell material | |
| CN111662705A (en) | Method for improving stability of perovskite | |
| CN111944159A (en) | Zinc-based flaky metal organic framework particle material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220128 |
|
| RJ01 | Rejection of invention patent application after publication |