CN111569860A - Preparation method and application of Z-scheme type perovskite quantum dot/bismuth tungstate composite material - Google Patents
Preparation method and application of Z-scheme type perovskite quantum dot/bismuth tungstate composite material Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 43
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002096 quantum dot Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 239000002135 nanosheet Substances 0.000 claims abstract description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 claims abstract description 8
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- IWDXBHSUFKRAQP-UHFFFAOYSA-N [Cs].[Pb] Chemical compound [Cs].[Pb] IWDXBHSUFKRAQP-UHFFFAOYSA-N 0.000 claims description 11
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 9
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000006798 recombination Effects 0.000 claims description 5
- 238000005215 recombination Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- -1 octadecylene Chemical group 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000002064 nanoplatelet Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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Abstract
The invention discloses Z-scheme type cesium lead bromide (CsPbBr)3) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) A method for preparing a nano-sheet compound, belongs to the technical field of composite materials, and relates to CsPbBr3Perovskite quantum dots and Bi2WO6A method of preparing a nanoplatelet composite comprising the steps of: adding Bi2WO6Ultrasonically dissolving the nanosheet solid in ethyl acetate to obtain a solution A; reacting CsPbBr3Adding the quantum dot solution into the solution A to form a mixed solution A; mixing the mixed solution A with Bi in an ultrasonic machine2WO6The nanosheet ultrasonic wave is designed to promote separation of photo-generated electrons and holes and maintain CsPbBr3Higher reduction driving force of conduction band electrons, and improved CsPbBr3Stability and catalytic activity of the invention, and CsPbBr of the invention3Quantum dots and Bi2WO6The stability and catalytic activity of the perovskite are improved by the composite formed by connecting the nano sheets through Bi-Br bonds, and the method also has the advantages of simple preparation process, low price, popularization of a technical route and the like.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method and application of a Z-scheme type cesium lead bromoperovskite and bismuth tungstate nanosheet compound.
Background
Fossil energy depletion and greenhouse gas effect are two major problems facing human development. Solar energy is inexhaustible clean energy, is inspired by photosynthesis, and utilizes the solar energy to carry out a photocatalytic process on carbon dioxide (CO)2) Conversion to high value-added industrial chemicals and fuels is considered to be an ideal way to solve the above problems. In this context, TiO is used2、ZnO、CdS、WO3A number of photocatalytic systems with ultraviolet or visible light response have been developed to carry out CO2The transformation of (3). However, these catalysts have limitations such as absorption of ultraviolet light, susceptibility to photo-corrosion, or severe recombination of photo-generated carriers, which greatly limit the development and wide application of the photocatalyst. Therefore, development of inexpensive materials having strong visible light absorption for photocatalysis is urgently required. Perovskite materials, in particular fully inorganic CsPbBr3Perovskites are expected to be ideal semiconductor catalysts due to their unique optoelectronic properties, and such semiconductors have exhibited very good properties in the fields of solar cells, LED displays, and the like.
Compared to the excellent properties exhibited in solar cells and LED displaysPure CsPbBr3The inorganic perovskite catalyst is still low in catalytic property and poor in stability, and cannot meet industrial application. This is mainly caused by two reasons: (1) for pure CsPbBr3The photoexcited electron-hole radiation recombination is serious, and the utilization efficiency of photon-generated carriers is low; (2) the hole transport rate is slow and the corresponding oxidation reaction cannot effectively occur on the surface of the perovskite, thereby limiting the overall reaction rate. Conventional methods for improving catalyst properties typically require compositing the perovskite with other catalysts having lower conduction band or reduction potential to facilitate electron transport of the perovskite to these catalysts, which tends to lower the reduction potential of the photo-generated electrons, and is thermodynamically unfavorable for improving catalytic efficiency.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a Z-scheme type cesium lead bromine perovskite and bismuth tungstate nanosheet compound, which can promote the separation of photoproduction electrons and holes, can keep higher reduction driving force of cesium lead bromine conduction band electrons, improves the stability and catalytic activity of cesium lead bromine, and has the advantages of simple preparation process, low price, popularization of a technical route and the like.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of a Z-scheme type cesium-lead-bromine perovskite and bismuth tungstate nanosheet compound comprises the following steps:
s1, ultrasonically dissolving a bismuth tungstate nanosheet solid in ethyl acetate to obtain a solution A;
s2, adding the cesium-lead-bromine quantum dot solution into the solution A to form a mixed solution A;
and S3, carrying out ultrasonic recombination on the mixed solution A in an ultrasonic machine for 0.5h to form a heterojunction.
Further, the ratio of the cesium-lead bromide quantum dots to the bismuth tungstate nanosheets is 1 g: 5g of the total weight.
Further, in S1, the preparation method of the bismuth tungstate nanosheet includes the following steps:
s11: adding a tungsten source compound, a bismuth source compound and hexadecyl trimethyl ammonium bromide into the aqueous solution, stirring for 0.5h, and fully reacting to obtain a mixed solution B;
s12: adding the mixed solution B prepared in the step S11 into a stainless steel reaction kettle, and reacting at 120 ℃ for 24 hours to obtain a mixed solution C;
s13: and (3) centrifugally washing the mixed solution C prepared in the S12 with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, and drying at 60 ℃ for 10 hours to obtain a solid, namely the bismuth tungstate nanosheet.
Further, the tungsten source compound is sodium tungstate dihydrate, and the bismuth source compound is bismuth nitrate pentahydrate;
the molar ratio of the tungsten source compound, the bismuth source compound and CTAB in S11 is 1:2: 0.15.
Further, in S2, the preparation method of the cesium lead bromoperovskite quantum dot includes the following steps:
s21: adding a cesium source compound and oleic acid into octadecene, heating to 120 ℃ in an argon atmosphere, and fully reacting to obtain a mixed solution D;
s22: adding a compound which is a lead source and a bromine source, oleic acid and oleylamine into octadecylene, heating to 165 ℃, and fully reacting to obtain a mixed solution E;
s23: adding a proper amount of the mixed solution D obtained in the step S21 into the mixed solution E obtained in the step S22, stirring for 5 seconds, putting into an ice-water bath, and then performing centrifugal separation to obtain a solid, namely the cesium-lead-bromine quantum dots of the oil phase;
s24: and (4) dispersing the cesium lead bromine quantum dots prepared in the step (3) in ethyl acetate to obtain liquid, namely the cesium lead bromine perovskite quantum dots.
Further, the cesium source compound is cesium carbonate, and the compound of the lead source and the bromine source is lead bromide;
the ratio of the cesium source compound to the oleic acid and the octadecene in the mixed solution A is 2.5 mol: 2.5L: 40L;
the proportion of the mixed liquid B of lead bromide to oleic acid, oleylamine and octadecene is 1.88 mol: 10L: 5.5L: 50L;
in the step 3, the ratio of the cesium source compound to the lead bromide is 1 mol: 3.7 mol;
the CsPbBr3The ratio of quantum dots to toluene was 8 g: 1L of the compound.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) the invention uses CsPbBr3The quantum dots and the bismuth tungstate nano-sheets are compounded to form a Z-scheme heterojunction, and the design can promote the separation of photoproduction electrons and holes and can also keep CsPbBr3Higher reduction driving force of conduction band electrons, and improves CsPbBr3Stability and catalytic activity of. Meanwhile, the method also has the advantages of simple preparation process, low price, popularization of technical route and the like.
(2) CsPbBr of the invention3Quantum dots and Bi2WO6The stability and the catalytic activity of the perovskite are improved by a compound formed by connecting the nano sheets through Bi-Br bonds.
(3) CsPbBr of the invention3-Bi2WO6The Z-scheme heterojunction maintains higher conduction band reduction capability and valence band oxidation capability, and provides convenience for synthesizing a novel Z-scheme heterojunction.
Drawings
FIG. 1 is a schematic diagram of the synthesis and recombination process of cesium-lead-bromoperovskite quantum dots and bismuth tungstate nanosheets of the present invention;
FIG. 2 is a schematic view of a Transmission Electron Microscope (TEM) of a bismuth tungstate nano-sheet of the present invention;
FIG. 3 is a schematic view of a Transmission Electron Microscope (TEM) of cesium lead bromoperovskite quantum dots of the present invention;
FIG. 4 shows CsPbBr of the present invention3、Bi2WO6And CsPbBr3-Bi2WO6XRD pattern of (a);
FIG. 5 shows CsPbBr of the present invention3、Bi2WO6And CsPbBr3-Bi2WO6(CPB-BWO) photocatalytic property profile;
FIG. 6The Z-scheme type CsPbBr is the invention3-Bi2WO6Stability schematic of the composite catalyst for photocatalytic reduction of carbon dioxide.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top/bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are to be construed broadly, e.g., "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1:
referring to fig. 1 to 4, a method for preparing a Z-scheme type cesium lead bromoperovskite and bismuth tungstate nanosheet composite is characterized in that: the method comprises the following steps:
s1, ultrasonically dissolving a bismuth tungstate nanosheet solid in ethyl acetate to obtain a solution A;
s2, adding the cesium-lead-bromine quantum dot solution into the solution A to form a mixed solution A;
s3, compounding the mixed solution A in an ultrasonic machine for 0.5h to form a heterojunction,
the ratio of the cesium-lead-bromine quantum dots to the bismuth tungstate nano-sheets is 1 g: 5g of the total weight. As shown in fig. 1, a schematic diagram of a preparation process of the cesium lead bromoperovskite and bismuth tungstate nanosheet composite is shown.
In S1, a method for preparing bismuth tungstate nanoplates includes the steps of:
s11: adding a tungsten source compound, a bismuth source compound and hexadecyl trimethyl ammonium bromide into the aqueous solution, stirring for 0.5h, and fully reacting to obtain a mixed solution B;
s12: adding the mixed solution B prepared in the step S11 into a stainless steel reaction kettle, and reacting at 120 ℃ for 24 hours to obtain a mixed solution C;
s13: centrifugally washing the mixed solution C prepared in the S12 with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, drying at 60 ℃ for 10 hours to obtain a solid, namely a bismuth tungstate nano-sheet,
the tungsten source compound is sodium tungstate dihydrate (Na)2WO4·2H2O), the bismuth source compound is bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O)；
In the step 1, the molar ratio of the tungsten source compound, the bismuth source compound and CTAB is 1:2: 0.01. As shown in fig. 2, is a schematic view of a Transmission Electron Microscope (TEM) of bismuth tungstate nanosheets.
In S2, the method for preparing the cesium lead bromoperovskite quantum dot includes the following steps:
s21: adding a cesium source compound and oleic acid into octadecene, heating to 120 ℃ in an argon atmosphere, and fully reacting to obtain a mixed solution D;
s22: adding a compound which is a lead source and a bromine source, oleic acid and oleylamine into octadecylene, heating to 165 ℃, and fully reacting to obtain a mixed solution E;
s23: adding a proper amount of the mixed solution D obtained in the step S21 into the mixed solution E obtained in the step S22, stirring for 5 seconds, putting into an ice-water bath, and then performing centrifugal separation to obtain a solid, namely the cesium-lead-bromine quantum dots of the oil phase;
s24: dispersing the cesium lead bromine quantum dots prepared in the step (3) in ethyl acetate to obtain liquid, namely the cesium lead bromine perovskite quantum dots,
the cesium source compound is cesium carbonate, and the lead source and bromine source compound is lead bromide;
the ratio of the cesium source compound to oleic acid and octadecene in the mixed solution A is 2.5 mol: 2.5L: 40L;
the proportion of the mixed solution B of lead bromide to oleic acid, oleylamine and octadecene is 1.88 mol: 10L: 5.5L: 50L;
in the step 3, the ratio of the cesium source compound to the lead bromide is 1 mol: 3.7 mol;
CsPbBr3the ratio of quantum dots to toluene was 8 g: 1L of the compound.
Example 2:
referring to FIGS. 1-4, CsPbBr3Quantum dots and Bi2WO6The preparation method of the Z-scheme heterojunction formed by the nanosheets comprises the following steps:
2mg of oil phase cesium lead bromide quantum dots prepared by high temperature thermal injection (synthesized as described in the section "supporting information" of Wang, H.; Wan, S.; Zhong, Q.; Xu, R.amino-Assisted irradiation of CsPbBr)3Perovskite QuantumDots on Porous g-C3N4for Enhanced Photocatalytic CO2Reduction. angelw. chem. int.ed.2018,130,13758-13762) in 2mL of toluene, followed by the addition of 10mg of sonicated Bi2WO6 nanoplates (synthesized as described in the following article: zhou, y.; zhang, y.; lin, m.; long, j.; zhang, z.; lin, H.; wu, j.c.; wang, x.nat. commun.2015,6,8340.)10mL of ethyl acetate solution, sonicated for 0.5 h; centrifugation and air drying gave a pale yellow solid powder. CsPbBr prepared as shown in FIG. 43-Bi2WO6X-ray diffraction pattern of complex (CPB-BWO).
Example 3:
please refer to FIG. 5, Z-scheme type CsPbBr3-Bi2WO6The composite catalyst is used for photocatalytic reduction of carbon dioxide:
CsPbBr prepared in example 1 was weighed3-Bi2WO65mg of the complex was dissolved in 5mL of ethyl acetate, 30. mu.L of deionized water was added thereto, and the mixture was transferred to a 30mL reactor into which carbon dioxide gas was introduced. A 300W xenon lamp is used as a light source, and sunlight is simulated to carry out a photocatalytic carbon dioxide reduction experiment, as shown in figure 3; samples were taken periodically and the resulting carbon monoxide and methane content were analyzed by gas chromatography.
Example 4:
please refer to FIG. 6, Z-scheme type CsPbBr3-Bi2WO6Stability of the composite catalyst in photocatalytic reduction of carbon dioxide:
CsPbBr prepared in example 1 was weighed3-Bi2WO65mg of the complex was dissolved in 5mL of ethyl acetate, 30. mu.L of deionized water was added thereto, and the mixture was transferred to a 30mL reactor into which carbon dioxide gas was introduced. A 300W xenon lamp is used as a light source, and sunlight is simulated to carry out a photocatalytic carbon dioxide reduction experiment, as shown in FIG. 6; samples were taken periodically and the resulting carbon monoxide and methane content were analyzed by gas chromatography. The above operation was repeated at two hour intervals. Four cycles were repeated to check the stability.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (10)
1. Z-scheme type cesium lead bromide (CsPbBr)3) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) The preparation method of the nano-sheet compound is characterized by comprising the following steps: the method comprises the following steps:
s1, ultrasonically dissolving a bismuth tungstate nanosheet solid in ethyl acetate to obtain a solution A;
s2, adding the cesium-lead-bromine quantum dot solution into the solution A to form a mixed solution A;
and S3, carrying out ultrasonic recombination on the mixed solution A in an ultrasonic machine for 0.5h to form a heterojunction.
2. A Z-scheme type cesium lead bromide (CsPbBr) according to claim 13) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) The preparation method of the nano-sheet compound is characterized by comprising the following steps: the ratio of the cesium-lead-bromine quantum dot to the bismuth tungstate nanosheet solid is 1 g: 5g of the total weight.
3. A Z-scheme type cesium lead bromide (CsPbBr) according to claim 13) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) The preparation method of the nano-sheet compound is characterized by comprising the following steps: in S1, the preparation method of the bismuth tungstate nano-sheet comprises the following steps:
s11: adding a tungsten source compound, a bismuth source compound and hexadecyl trimethyl ammonium bromide into the aqueous solution, stirring for 0.5h, and fully reacting to obtain a mixed solution B;
s12: adding the mixed solution B prepared in the step S11 into a stainless steel reaction kettle, reacting for 24 hours at the temperature of 120 ℃, and fully reacting to obtain a mixed solution C;
s13: and (3) centrifugally washing the mixed solution C prepared in the step S12 with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, and drying at 60 ℃ for 10 hours to obtain a solid, namely the bismuth tungstate nanosheet.
4. The method and the device for preparing the cesium lead bromoperovskite and bismuth tungstate nano-sheets according to claim 3, wherein the method comprises the following steps:
the tungsten source compound is sodium tungstate dihydrate, and the bismuth source compound is bismuth nitrate pentahydrate;
in the S11, the molar ratio of the tungsten source compound to the bismuth source compound to CTAB is 1:2: 0.15.
5. A Z-scheme type cesium lead bromide (CsPbBr) according to claim 13) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) The preparation method of the nano-sheet compound is characterized in thatIn the following steps: in the S2, the preparation method of the cesium lead bromine perovskite quantum dot comprises the following steps:
s21: adding a cesium source compound and oleic acid into octadecene, heating to 120 ℃ in an argon atmosphere, and fully reacting to obtain a mixed solution D;
s22: adding a compound which is a lead source and a bromine source, oleic acid and oleylamine into octadecylene, heating to 165 ℃, and fully reacting to obtain a mixed solution E;
s23: adding a proper amount of the mixed solution D obtained in the step S21 into the mixed solution E obtained in the step S22, stirring for 5 seconds, then placing into an ice water bath for cooling, and centrifuging to obtain a solid, namely the cesium-lead-bromine quantum dots of the oil phase;
s24: and (3) dispersing the cesium lead bromine quantum dots prepared in the step (S23) in toluene to obtain liquid, namely the cesium lead bromine perovskite quantum dots.
6. A Z-scheme type cesium lead bromide (CsPbBr) according to claim 53) Perovskite quantum dots and bismuth tungstate (Bi)2WO6) The preparation method of the nano-sheet compound is characterized by comprising the following steps: the cesium source compound is cesium carbonate, and the lead source and bromine source compound is lead bromide.
7. The method for preparing the Z-scheme type cesium lead bromoperovskite and bismuth tungstate nano-sheet composite as claimed in claim 5, wherein the method comprises the following steps: the ratio of the cesium source compound to oleic acid and octadecene in the mixed solution D is 2.50 mol: 2.5L: 40L.
8. The method for preparing the Z-scheme type cesium lead bromoperovskite and bismuth tungstate nano-sheet composite as claimed in claim 5, wherein the method comprises the following steps: the proportion of the mixed solution E of lead bromide to oleic acid, oleylamine and octadecene is 1.88 mol: 10L: 5.5L: 50L.
9. The method for preparing the Z-scheme type cesium lead bromoperovskite and bismuth tungstate nano-sheet composite as claimed in claim 5, wherein the method comprises the following steps: the ratio of the cesium source compound to the lead bromide in S23 is 1 mol: 3.7 mol.
10. The method for preparing the Z-scheme type cesium lead bromoperovskite and bismuth tungstate nano-sheet composite as claimed in claim 5, wherein the method comprises the following steps: the ratio of the cesium-lead-bromine quantum dot to toluene is 8 g: 1L of the compound.
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