CN112892561A - Lead-free bismuth-based mixed halogenated perovskite nanosheet and preparation method and application thereof - Google Patents
Lead-free bismuth-based mixed halogenated perovskite nanosheet and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 43
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- 230000001699 photocatalysis Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002055 nanoplate Substances 0.000 claims description 6
- 239000012296 anti-solvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002105 nanoparticle Substances 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- B01J27/08—Halides
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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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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- C07C201/06—Preparation of nitro compounds
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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Abstract
The invention discloses a lead-free bismuth-based mixed halogenated perovskite nanosheet and a preparation method and application thereof3Bi2‑xSbxBr9Nanosheets having a molecular formula of Cs3Bi2‑xSbxBr9And x is less than or equal to 0.4 in the formula < 0 >. Introduction of Sb increased Cs3Bi2Br9Visible light absorption capability and photogenerated carrier separation efficiency. Good size matching of Sb improves Cs3Bi2Br9Stability of the perovskite material. The small amount of Sb doping promotes C (sp)3) The H bond activates the generation of a hole of a key active species.
Description
Technical Field
The invention relates to the technical field of nano material preparation and photocatalysis, in particular to a lead-free bismuth-based mixed halogenated perovskite nanosheet, a preparation method thereof and application thereof in photocatalysis C (sp)3) -H bond activation.
Background
The selective oxidation of saturated hydrocarbons to produce high value added products (e.g., aldehydes, ketones, and epoxides) is one of the most challenging and interesting disciplines in catalytic chemistry today. Due to C (sp)3) -H bond (70-130 kcalmol)-1) High bond dissociation energy and unfavorable adsorption, often requiring harsh conditions (high temperature and/or pressure). In addition, the conversion rate must be suppressed to less than<15% to avoid over oxidation of the product under such harsh conditions resulting in poor selectivity. To solve this problem, replacing traditional thermal catalysis with mild photocatalysis is a promising solution. Heterogeneous photocatalytic systems of metal oxides and metal sulfides have now led to an extensive search by researchers due to their high stability and ease of separationAttention is paid. However, the performance of these photocatalysts is still not ideal due to narrow light absorption, low charge separation efficiency and conversion efficiency. All-metal halide perovskite AIPbIIX3(A ═ Rb, Cs; B ═ Ge, Pb, Sn; and X ═ Cl, Br, I), in particular CsPbBr3And CsPbI3It has proven to be a promising photocatalytic material due to its appropriate bandgap, excellent light absorption and efficient carrier mobility. However, the use of lead in the field of photocatalysis is limited due to its toxicity, low oxidation capacity (valence band top is typically less than 1.4eV) and chemical stability.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a lead-free bismuth-based mixed halogenated perovskite nanosheet and a preparation method and application thereof. The Sb doping improves the separation efficiency of the catalyst on the photo-generated carriers absorbed by visible light on one hand, and promotes the generation of holes on the other hand. At the same time, good size matching of Sb improves Cs3Bi2Br9Stability of the perovskite material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
lead-free bismuth-based mixed halogenated perovskite nanosheet with molecular formula of Cs3Bi2-xSbxBr9And x is less than or equal to 0.4 in the formula < 0 >.
Preferably, x is more than or equal to 0.1 and less than or equal to 0.3 in the molecular formula; further preferably, x is 0.2.
The invention also provides a preparation method of the lead-free bismuth-based mixed halogenated perovskite nanosheet, which comprises the following steps:
(1) according to a set molar ratio, CsBr and BiBr are added3And SbBr3Dissolving in DMSO to obtain precursor solution;
(2) adding the precursor liquid obtained in the step (1) into isopropanol, crystallizing for 0.5-5 min by an anti-solvent method, and washing and drying to obtain Cs3Bi2-xSbxBr9Nanosheets.
Preferably, the BiBr in step (1)3And SbBr3The molar ratio of (1.7: 0.3) - (1.9: 0.1), and the concentration of CsBr in DMSO is 10-20 mM.
Further preferably, the BiBr is3And SbBr3The molar ratio of (A) to (B) is 1.8: 0.2.
Preferably, the volume ratio of the precursor liquid to the isopropanol in the step (2) is 1: 20-1: 30.
Preferably, in the step (2), the Cs is obtained by washing with chloroform and then drying in a vacuum oven at 60 ℃ for 10 hours3Bi2-xSbxBr9Nanosheets.
The invention also provides application of the lead-free bismuth-based mixed halogenated perovskite nanosheet in photocatalysis of C (sp)3) -H bond activation reaction.
The invention adopts Bi and Sb as B-site cations in halide perovskite, wherein Bi is used as a main element, Sb is used as an auxiliary element, and the mixed halide perovskite nanosheet is synthesized by an anti-solvent recrystallization method. The inventors have found that during the anti-solvent process, the crystallization time needs to be strictly controlled so as not to form large crystal particles and not to obtain the nanoplatelets of the present invention. The invention is realized by adding Cs3Bi2Br9A small amount of Sb is introduced to replace part of Bi, and the doping of Sb improves the separation efficiency of the catalyst on the photo-generated carriers absorbed by visible light on one hand and promotes the generation of holes on the other hand. At the same time, good size matching of Sb improves Cs3Bi2Br9Stability of the perovskite material.
Compared with the prior art, the invention has the advantages that:
the invention prepares Cs by a simple anti-solvent recrystallization method3Bi2-xSbxBr9Nanosheet, introduction of Sb increases Cs3Bi2Br9Visible light absorption capability and photogenerated carrier separation efficiency. Good size matching of Sb improves Cs3Bi2Br9Stability of the perovskite material. A small amount of Sb doping promotesC(sp3) The H bond activates the generation of a hole of a key active species.
Drawings
FIG. 1 shows Cs samples obtained in comparative example 1, example 1 and comparative examples 2 to 43Bi2Br9(a)、Cs3Bi1.8Sb0.2Br9(b)、Cs3Bi1.5Sb0.5Br9(c)、Cs3Bi0.7Sb1.3Br9(d)、Cs3Sb2Br9(e) SEM image of (d).
FIG. 2 is an SEM photograph of samples prepared in example 1(a), comparative example 5(b), and comparative example 6 (c).
FIG. 3 is an SEM photograph of samples prepared in example 1(a), comparative example 7(b), and comparative example 8 (c).
FIG. 4 shows Cs samples obtained in comparative example 1, example 1 and comparative examples 2 to 43Bi2Br9、Cs3Bi1.8Sb0.2Br9、Cs3Bi1.5Sb0.5Br9、Cs3Bi0.7Sb1.3Br9、Cs3Sb2Br9XRD pattern of (a).
FIG. 5 shows Cs samples obtained in comparative example 1, example 1 and comparative examples 2 to 43Bi2Br9、Cs3Bi1.8Sb0.2Br9、Cs3Bi1.5Sb0.5Br9、Cs3Bi0.7Sb1.3Br9、Cs3Sb2Br9Performance testing of photocatalytic toluene oxidation.
FIG. 6 shows Cs obtained in comparative example 1 and example 13Bi2Br9、Cs3Bi1.8Sb0.2Br9Stability of the samples is compared.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The invention is based on the photocatalysis of C (sp)3) Evaluation of-H bond activationCs3Bi2-xSbxBr9Activity of the nanoplatelets. Firstly, dispersing 10mg of catalyst into 5mL of reaction substrate; the mixture was magnetically stirred in the dark for 30min and oxygen (2mL min)-1) The bottom of the reaction mixture was introduced and the adsorption-desorption equilibrium was established. A300W xenon lamp is adopted as a light source and is provided with a lambda filter with the wavelength being more than or equal to 400 nm. Quantitative analysis was carried out by gas chromatography using an internal standard method.
Example 1
Cs3Bi1.8Sb0.2Br9Preparing a nano sheet:
0.45mmol CsBr and 0.075mmol SbBr3And 0.225mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi1.8Sb0.2Br9Nanosheets.
Comparative example 1
Cs3Bi2Br9Preparing a nano sheet:
adding 0.45mmol CsBr and 0.30mmol BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi2Br9Nanosheets.
Comparative example 2
Cs3Bi1.5Sb0.5Br9Preparing a nano sheet:
0.45mmol CsBr and 0.150mmol SbBr3And 0.150mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi1.5Sb0.5Br9Nanosheets.
Comparative example 3
Cs3Bi0.7Sb1.3Br9Preparing nano particles:
0.45mmol CsBr and 0.225mmol SbBr3And 0.075mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi0.7Sb1.3Br9And (3) nanoparticles.
Comparative example 4
Cs3Sb2Br9Preparing nano particles:
0.45mmol CsBr and 0.30mmol SbBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi2Br9And (3) nanoparticles.
Comparative example 5
Cs3Bi1.8Sb0.2Br9Preparing nano particles:
0.45mmol CsBr and 0.075mmol SbBr3And 0.225mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 180 min. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi1.8Sb0.2Br9And (3) nanoparticles.
Comparative example 6
Cs3Bi1.8Sb0.2Br9Preparing nano particles:
0.45mmol CsBr and 0.075mmol SbBr3And 0.225mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 720 min. Washing with chloroform for three times, and drying in a vacuum oven at 60 deg.C for 10 hr to obtain yellowColor Cs3Bi1.8Sb0.2Br9And (3) nanoparticles.
Comparative example 7
Cs3Bi1.8Sb0.2Br9Preparing nano particles:
2.25mmol CsBr, 0.375mmol SbBr3And 1.125mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi1.8Sb0.2Br9And (3) nanoparticles.
Comparative example 8
Cs3Bi1.8Sb0.2Br9Preparing nano particles:
4.5mmol CsBr, 0.75mmol SbBr3And 2.25mmol of BiBr3Dissolved in 30mL of DMSO to obtain a precursor liquid. Then, 2mL of precursor was added to 50mL of isopropanol with vigorous stirring, and stirred rapidly for 1 minute. Washed three times with chloroform and dried in a vacuum oven at 60 ℃ for 10 hours to obtain yellow Cs3Bi1.8Sb0.2Br9And (3) nanoparticles.
Performance evaluation:
by photocatalysis of C (sp)3) H bond activation the catalytic activity of the prepared samples was investigated for model reactions:
10mg of the sample was dispersed in 5mL of toluene. The mixture was magnetically stirred in the dark for 30min and oxygen (2mL min)-1) The bottom of the reaction mixture was introduced and the adsorption-desorption equilibrium was established. A300W xenon lamp is adopted as a light source and is provided with a lambda filter with the wavelength being more than or equal to 400 nm. The amounts of reactants and products were determined by internal standard method with n-decane as internal standard. Quantitation was performed on a Shimadzu GC2010Plus chromatograph equipped with a FID detector and a WAX capillary column (30 m. times.0.25 mm. times.0.25 μm).
The results of the photocatalytic toluene oxidation reaction of the samples obtained in example 1 and comparative examples 1 to 4 are shown in table 1:
TABLE 1 results of photocatalytic toluene oxidation reaction of samples prepared in example 1 and comparative examples 1 to 4
As is clear from Table 1, different toluene conversion rates were obtained at different molar ratios of Bi and Sb, wherein the molar ratio of Bi to Sb was 1.8:0.2, and the formation rates of benzaldehyde and benzyl alcohol were 4.033mmol g-1h-1And 1.779mmol g-1h-1The best photocatalysis effect.
TABLE 2 results of photocatalytic toluene oxidation reaction of samples obtained in example 1 and comparative examples 5 to 6
As can be seen from Table 2, different toluene conversion rates were obtained at different crystallization times, wherein the benzaldehyde and benzyl alcohol formation rates at 1min were 4.033mmol g-1h-1And 1.779mmol g-1h-1The best photocatalysis effect.
TABLE 3 results of photocatalytic toluene oxidation reaction of samples obtained in example 1 and comparative examples 7 to 8
As can be seen from Table 3, CsBr concentration in DMSO gave different toluene conversion rates, wherein the benzaldehyde and benzyl alcohol formation rates were 4.033mmol g for 1min-1h-1And 1.779mmol g-1h-1The best photocatalysis effect.
Toluene derivatives having other substituents were tested on the samples prepared in example 1, and the results are shown in Table 4:
TABLE 4 results of photocatalytic oxidation of toluene derivatives for samples obtained in example 1
Note:areaction conditions are as follows: 5mL substrate, 10mg Cs3 Bi1.8Sb0.2Br9As photocatalyst, lambda is more than or equal to 400nm, O2(2mL·min-1) And the reaction time is 3 hours.bSolid p-nitrotoluene (3.225g, relative density 1.29g mL)-1) Dissolved in 2.5mL acetonitrile for reaction.
As shown in FIG. 1a, Cs3Bi2Br9In the form of nanoplates, having a thickness of about 20 nm. Substituted by small amounts of Sb (Cs)3Bi1.8Sb0.2Br9And Cs3Bi1.5Sb0.5Br9) The sheet structure can be maintained (fig. 1b and 1 c). However, the content of Sb, Cs, was further increased3Bi0.7Sb1.3Br9Shown as nanoparticles (FIG. 1d), this is in contrast to pure Cs3Sb2Br9(FIG. 1e) are identical.
As shown in FIG. 2, Cs at different crystallization times3Bi1.8Sb0.2Br9The morphology of (A) is very different. Crystallization 1min for nanoplatelets (2a), crystallization 180min for nanoparticles (2b), and crystallization 700min for larger nanoparticles (2 c).
As shown in FIG. 3, the Cs obtained at different concentrations of CsBr in DMSO3Bi1.8Sb0.2Br9The morphology of (A) is very different. Nanosheets (3a) at a concentration of 15mM, nanoparticles (3b) at a concentration of 75mM and nanoparticles (3c) of larger size at a concentration of 150 mM.
As shown in FIG. 4a, with Cs3Bi2Br9In contrast, Cs increased with Sb content3Bi2Br9The diffraction peaks in (003), (300) and (220) gradually decrease in position and are in Cs3Sb2Br9Middle disappearance (Miao Xiao)While the characteristic peaks of (022) and (204) are at a larger angle (fig. 4 b).
As shown in FIG. 5, the conversion of toluene was dependent on Sb3+The increase in (c) increases first and then decreases. In Cs3Bi1.8Sb0.2Br9The nano-sheet has the highest conversion rate which reaches 5813 mu mol h-1g-1The selectivity of benzaldehyde and benzyl alcohol was 69.4% and 30.6%, respectively, and Cs3Bi1.8Sb0.2Br9Respectively about pure Cs3Sb2Br9And Cs3Bi2Br95.1 and 2.1 times.
As shown in FIG. 6, the cycling experiment showed that Cs3Bi1.8Sb0.2Br9The original activity retained after 4 cycles was over 77%, while Cs3Bi2Br9Only 50% of its original activity was retained.
Claims (9)
1. A lead-free bismuth-based mixed halogenated perovskite nanosheet is characterized in that: its molecular formula is Cs3Bi2-xSbxBr9And x is less than or equal to 0.4 in the formula < 0 >.
2. The lead-free bismuth-based mixed halogenated perovskite nanoplate as claimed in claim 1, characterized in that: x in the molecular formula is more than or equal to 0.1 and less than or equal to 0.3.
3. The lead-free bismuth-based mixed halogenated perovskite nanoplate as claimed in claim 2, characterized in that: in the formula, x is 0.2.
4. A method of producing lead-free bismuth-based mixed halogenated perovskite nanoplate as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
(1) according to a set molar ratio, CsBr and BiBr are added3And SbBr3Dissolving in DMSO to obtain precursor solution;
(2) adding the precursor liquid obtained in the step (1) into isopropanol, crystallizing for 0.5-5 min by an anti-solvent method, washing and drying to obtain the productCs3Bi2-xSbxBr9Nanosheets.
5. The method of claim 4, wherein: the BiBr in the step (1)3And SbBr3The molar ratio of (1.7: 0.3) - (1.9: 0.1), and the concentration of CsBr in DMSO is 10-20 mM.
6. The method of claim 5, wherein: the BiBr3And SbBr3Is 1.8: 0.2.
7. The method of claim 4, wherein: the volume ratio of the precursor liquid to the isopropanol in the step (2) is 1: 20-1: 30.
8. The method of claim 4, wherein: in the step (2), washing with chloroform, and then drying in a vacuum oven at 60 ℃ for 10 hours to obtain Cs3Bi2-xSbxBr9Nanosheets.
9. Use of the lead-free bismuth-based mixed halogenated perovskite nanoplate as defined in any one of claims 1 to 3 or the lead-free bismuth-based mixed halogenated perovskite nanoplate produced by the production method as defined in any one of claims 4 to 8, characterized in that: it is used for photocatalysis of C (sp)3) -H bond activation reaction.
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