CN112619709A - Photocatalytic nano material and preparation method thereof - Google Patents
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 51
- 239000002105 nanoparticle Substances 0.000 claims abstract description 45
- 150000004820 halides Chemical class 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 10
- -1 iron ion Chemical class 0.000 claims description 7
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- 229910001429 cobalt ion Inorganic materials 0.000 claims 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 238000010586 diagram Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention provides a mixed band gap halide perovskite nano material, which comprises a metal organic framework material and halide perovskite nano particles; the halide perovskite nano particles are embedded in the pore channels of the metal organic framework material; the metal organic framework material is a porous crystal material formed by metal transition ions and organic ligands; the band gap of the halide perovskite nano particles is gradually reduced from outside to inside; the surface layer of the perovskite nano particle is FAPBR3The kernel is FAPBI3. The photocatalytic nano material obviously improves the water vapor stability of halide perovskite nano particles; can efficiently absorb and utilize sunlight with different energies, and has higher conversion efficiency of light-chemical energy. The photocatalysis technology is in the field of environmental pollution, in particular to CO2The photocatalysis treatment has great application prospect. The invention also discloses a preparation method of the composition.
Description
Technical Field
The invention belongs to CO2The technical field of photocatalysis, in particular to a photocatalytic nano material and a preparation method thereof.
Background
While global warming is becoming a more and more widespread concern, CO2The emission reduction becomes a hot topic, because the future and fate of human living environment are concerned, the direct light-driven carbon dioxide emission reduction is a fascinating technology for using high-value-added chemical raw materials or fuel of high-efficiency catalysts. One of the most crucial challenges in artificial photosynthesis is the design of efficient and low cost catalysts and photosensitizers. In this context, a series of semiconductor nanocrystals have been sought as photosensitizers because of their large extinction coefficient, thermodynamically flexible control, and size of optical properties under particle control. Halide perovskite as a novel photoelectric functional material has extensive research in the fields of solar cells, light-emitting diodes, photodetectors, photoelectrocatalysis and the like, and remarkable research progress is achieved. Due to the advantages of low cost, simple synthesis method and the like, the perovskite also has very wide application prospect in the field of photocatalytic carbon dioxide reduction.
However, the stability and "photo-chemical energy" conversion efficiency of photocatalytic materials become a challenge.
Disclosure of Invention
The invention provides a novel photocatalytic nano material.
A photocatalytic nanomaterial comprising a metal-organic framework material, and halide perovskite nanoparticles; the halide perovskite nano particles are embedded in the pore channels of the metal organic framework material;
the metal organic framework material is a porous crystal material formed by metal transition ions and organic ligands;
the band gap of the halide perovskite nano particles is gradually reduced from outside to inside; preferably, the surface layer of the perovskite nano particle is FAPBBr3The kernel is FAPBI3。
According to the photocatalytic nano material, halide perovskite nano particles are embedded in the pore channels of the metal organic framework material, so that the water vapor stability of the halide perovskite nano particles is obviously improved; the band gap of the halide perovskite nano particles is gradually reduced from outside to inside, sunlight with different energies can be efficiently absorbed and utilized, and the halide perovskite nano particles have high photo-chemical energy conversion efficiency.
In one embodiment, the halide perovskite nanoparticles have the general chemical formula FApB (I)1- xBrx)3Wherein x is more than or equal to 0 and less than or equal to 1.
In one specific embodiment, the transition metal ions are zinc ions, and the organic ligand is a porphyrin organic substance or an imidazole organic substance.
The invention also provides a preparation method of the photocatalytic nano material.
A preparation method of a photocatalytic nano material comprises the following steps:
preparing metal organic framework materials MOFs;
loading PbI on the metal-organic framework material2To obtain a first product PbI2@MOFs；
Subjecting the first product PbI2@ MOFs; reacting with FAI to obtain a second product FAPBI3@MOFs；
The second product FAPBI3Ion exchange treatment is carried out on @ MOFs and FABr to obtain FAPb (I) with mixed band gap1-xBrx)3@ MOFs perovskite nanomaterials.
The photocatalytic nano material obtained by the preparation method obviously improves the water vapor stability of the halide perovskite nano particles; can efficiently absorb and utilize sunlight with different energies, and has higher conversion efficiency of light-chemical energy.
In one embodiment, the step of ion-exchanging the second product with FABr comprises: soaking the second product in FABr solution.
In one embodiment, the FABr solution is an isopropanol solution of FABr; the concentration of the FABr is 18g/L-22 g/L.
In one embodiment, the soaking time is 1-20 min.
In one embodiment, the metal organic framework material is synthesized by hydrothermal reaction.
In one embodiment, the metal-organic framework material is loaded with PbI2Comprises the following steps: soaking the metal-organic framework material in PbI2One hour or more in solution.
In one embodiment, the step of reacting the first product with FAI comprises: soaking the first product in FAI solution for 8-12 min.
Drawings
Fig. 1 is a schematic structural diagram of a metal organic framework according to the present invention.
FIG. 2 is a schematic representation of halide perovskite nanoparticles of the present invention.
Fig. 3 is a band gap diagram of the halide perovskite nanoparticles of fig. 2.
Fig. 4 is a schematic structural diagram of the photocatalytic nanomaterial of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A photocatalytic nanomaterial comprising a metal-organic framework material, and halide perovskite nanoparticles; the halide perovskite nano particles are embedded in the pore channels of the metal organic framework material;
the metal organic framework material is a porous crystal material formed by metal transition ions and organic ligands; mixing and reacting soluble metal salt and imidazole compounds in an organic solvent to obtain the metal organic framework material, wherein the soluble metal salt is selected from one or more of soluble metal halide, soluble metal nitrate, soluble metal acetate and soluble metal sulfate.
As shown in FIG. 1, 11 is a transition metal ion, and 12 is an organic ligand. 11 and 12 form a metal organic framework by bonding.
The band gap of the halide perovskite nano particles is gradually reduced from outside to inside; the surface layer of the perovskite nano particle is FAPBR3The kernel is FAPBI3。
Fig. 2 is a schematic representation of a mixed band gap perovskite nanoparticle with x =1, i.e. Br only, and no I in its outermost layer 21; at its core 22, x =0, i.e. only I, without Br. Fig. 3 is a band gap diagram of the halide perovskite nanoparticles of fig. 2. Denoted by 21 is the outer band gap and denoted by 22 is the inner band gap.
Referring specifically to fig. 4, fig. 4 is a molecular structure diagram of the photocatalytic nanomaterial of the present invention. Halide perovskite nano particles are embedded in the pore channels of the metal organic framework material; namely, the metal organic framework material is coated outside the halide perovskite nano particles. Thus, the metal organic framework material protects the halide perovskite nano particles and improves the water vapor stability of the halide perovskite nano particles. The band gap of the halide perovskite nano particles is gradually reduced from outside to inside, and the outermost layer is pure FAPBBr3The band gap can reach 2.3eV, and FAPBI is arranged at the innermost core3The band gap is 1.48 eV. The mixed bandgap FAPBI1-xBrxThe @ ZIF-8 nano material can absorb sunlight in more energy ranges
The metal organic framework materials are generally abbreviated as MOFs. The metal in the metal-organic framework material may be Re, Co, Fe, Ni, Mn, Mo, W, Ru, Os, Rh, Ir, Pd, Zn, Cr, Cu, etc. Complexes include, but are not limited to, complexes functionalized with carboxyl, phosphate, amino, and like groups. The complex can be polypyridine complex, porphyrin complex, imidazole complex, thiol complex, nitrogen heterocyclic carbene complex or other complexes.
In one embodiment, the transition metal ions in the metal-organic framework material are zinc ions, and the organic ligand is a porphyrin organic substance or an imidazole organic substance. More preferably, the metal organic framework material is sodalite type zinc methylimidazolate (ZIF-8).
In one embodiment, the halide perovskite nanoparticles have the general chemical formula FApB (I)1- xBrx)3Wherein x is more than or equal to 0 and less than or equal to 1. With different positions and different values of x, the band gap of the halide perovskite gradually changes, so that light with different wavelength bands can be absorbed, and the conversion efficiency of light-chemical energy is higher.
According to the photocatalytic nano material, halide perovskite nano particles are embedded in the pore channels of the metal organic framework material, so that the water vapor stability of the halide perovskite nano particles is obviously improved; the band gap of the halide perovskite nano particles is gradually reduced from outside to inside, sunlight with different energies can be efficiently absorbed and utilized, and the halide perovskite nano particles have high photo-chemical energy conversion efficiency.
The invention also provides a preparation method of the photocatalytic nano material.
A preparation method of a photocatalytic nano material comprises the following steps:
mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain metal organic framework materials MOFs;
loading PbI on the metal-organic framework material2To obtain a first product PbI2@MOFs；
Subjecting the first product PbI2@ MOFs; reacting with FAI to obtain a second product FAPBI3@MOFs；
The second product FAPBI3@ MOFs andFABr is subjected to ion exchange treatment to obtain FApB (I) with mixed band gap1-xBrx)3@ MOFs perovskite nanomaterials.
Mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain a metal organic framework material; preferably, the metal organic framework material is synthesized by hydrothermal reaction.
Wherein, PbI is loaded2The purpose of (A) is to mix PbI2Is introduced into the pores of the metal organic framework material. Preferably, PbI is loaded on the metal-organic framework material2Comprises the following steps: soaking the metal-organic framework material in PbI2One hour or more in solution.
Wherein the first product is reacted with FAI for the purpose of embedding PbI in the pores of the metal-organic framework material2Reaction with FAI to make PbI2Transition to FAPBI3(ii) a And FAPBI3Still embedded in the pores of the metal organic framework material. Preferably, the step of reacting the first product with FAI comprises: soaking the first product in FAI solution for 8-12 min.
Wherein the purpose of the ion exchange treatment is to embed FAPBI in the pore channel of the metal organic framework material3The iodide ions in the nanoparticles are subjected to ion exchange with bromide ions, namely the bromide ions migrate into FAPBI3In nanoparticles, the original FAPBI3Iodine ions in the nano particles partially migrate, namely, part of iodine ions in the positions are changed into bromine ions, the surface layer migrates faster, the ion exchange is more substrate, and the inner layer migrates slower, the ion exchange is insufficient; thereby leading the surface layer of the halide perovskite nano particle to be FAPBR3The inner layer is FAPBI3The intermediate part between the two is a mixture of iodide ions and bromide ions, but the respective contents of the two in different regions are different, resulting in variable band gaps in the different regions, i.e. the band gaps of the halide perovskite nanoparticles.
Preferably, the step of subjecting the second product to ion exchange treatment with FABr comprises: soaking the second product in FABr solution.
More preferably, the FABr solution is an isopropanol solution of FABr; the concentration of the FABr is 18g/L-22 g/L.
In one embodiment, the soaking time is 10 min.
The photocatalytic nano material obtained by the preparation method obviously improves the water vapor stability of the halide perovskite nano particles; can efficiently absorb and utilize sunlight with different energies, and has higher conversion efficiency of light-chemical energy.
The invention is further illustrated by the following examples.
Example 1
Synthesizing a metal organic framework material ZIF-8:
717mg of Zn (NO)3)2•6H2O (zinc nitrate hexahydrate), 180mg of H-MeIM (2-methylimidazole) in 50mL of DMF; heating to 150 ℃ in a hydrothermal reaction kettle at a heating rate of 5 ℃/min, preserving heat for 24 hours, and naturally cooling to room temperature.
After removing the supernatant, 50mL of chloroform was added to give colorless crystal particles. And washing the colorless crystal particles with DMF for three times, and drying to obtain the metal organic framework material ZIF-8.
Preparing a first product:
soaking a metal organic framework material ZIF-8 in 1mmol/L PbI2In solution (solvent is a mixed solvent of DMF and ethanol with a ratio of 1: 9) for one hour. After filtration, the mixture is washed with a mixed solvent of DMF: ethanol =1:1 and dried to obtain a first product.
Preparing a second product:
and soaking the first product in 10mg/mL of an isopropanol solution of FAI, filtering after 10min, washing with isopropanol, and drying to obtain a second product.
Synthesis of the final product:
and soaking the second product in 20mg/mL isopropanol solution of FABr for 10min, filtering, washing with isopropanol, and drying to obtain the photocatalytic nanomaterial.
While the present application has been described with reference to exemplary embodiments thereof, it is to be understood that the present application is not limited to the disclosed embodiments, which are presented by way of illustration rather than of limitation, and that various modifications may be made by those skilled in the art without departing from the spirit and scope of the present application as defined by the appended claims.
Claims (10)
1. A photocatalytic nanomaterial is characterized by comprising a metal organic framework material and halide perovskite nanoparticles; the halide perovskite nano particles are embedded in the pore channels of the metal organic framework material;
the metal organic framework material is a porous crystal material formed by metal transition ions and organic ligands;
the band gap of the halide perovskite nano particles is gradually reduced from outside to inside;
the chemical general formula of the halide perovskite nano particles is FAPb (I)1-xBrx)3Wherein x is more than or equal to 0 and less than or equal to 1;
the halide perovskite nanoparticles have a band gap in the range of 1.48eV to 2.3 eV.
2. The photocatalytic nanomaterial of claim 1, wherein the surface layer of the perovskite nanoparticles is FAPBBr3The kernel is FAPBI3。
3. The photocatalytic nanomaterial according to claim 1, wherein the transition metal ion is one of zinc ion, iron ion, copper ion and cobalt ion, and the organic ligand is a porphyrin organic substance or an imidazole organic substance.
4. The photocatalytic nanomaterial of claim 1, wherein the metal-organic framework material is ZIF-8.
5. A preparation method of a photocatalytic nano material is characterized by comprising the following steps:
preparing a metal organic framework material;
loading PbI on the metal-organic framework material2To obtain a first product
(ii) subjecting the first product; reacting with FAI to obtain a second product;
and carrying out ion exchange treatment on the second product and FABr.
6. The preparation method according to claim 5, wherein the metal-organic framework is prepared by mixing and reacting a soluble metal salt and an imidazole compound in an organic solvent.
7. The method of claim 5, wherein the step of ion-exchanging the second product with FABr comprises: soaking the second product in FABr solution.
8. The production method according to claim 7, wherein the FABr solution is an isopropanol solution of FABr; the concentration of the FABr is 18g/L-22 g/L; the soaking time is 1-20 min.
9. The method according to claim 5, wherein the metal-organic framework material is loaded with PbI2Comprises the following steps: soaking the metal-organic framework material in PbI2One hour or more in solution.
10. The method of claim 5, wherein the step of reacting the first product with FAI comprises: soaking the first product in FAI solution for 8-12 min.
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| WO2023028644A1 (en) * | 2021-08-31 | 2023-03-09 | The University Of Queensland | A metal organic framework (mof) glass composite comprising metal halide perovskite |
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