CN116409812A - Preparation and application of perovskite quantum dot and cadmium zinc sulfur nanorod composite photocatalyst - Google Patents
Preparation and application of perovskite quantum dot and cadmium zinc sulfur nanorod composite photocatalyst Download PDFInfo
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- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical compound [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002073 nanorod Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000002096 quantum dot Substances 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 32
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 21
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 20
- 239000005642 Oleic acid Substances 0.000 claims description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- -1 cadmium zinc sodium Chemical compound 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 19
- 238000011065 in-situ storage Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 abstract 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910007609 Zn—S Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- C01G11/00—Compounds of cadmium
- C01G11/006—Compounds containing, besides cadmium, two or more other elements, with the exception of oxygen or hydrogen
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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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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Abstract
The invention relates to the technical field of photocatalysis, and discloses a perovskite quantum dot and cadmium zinc sulfur nanorod composite photocatalystThe preparation and application of the composite photocatalyst adopts an in-situ growth mode, specifically, the cadmium zinc sulfur nano rod (Cd 0.9 Zn 0.1 S NRs) powder is put into a precursor solution for preparing cesium lead bromine, and the cesium lead bromine quantum dots (CsPbBr) are prepared by a thermal injection mode 3 QDs) are grown on the cadmium zinc sulfur nanorods in situ, and are centrifuged, washed and dried to finally obtain cesium lead bromide and cadmium zinc sulfur (CsPbBr) 3 ‑Cd 0.9 Zn 0.1 S) a composite photocatalyst. In addition, by constructing a heterojunction, carbon dioxide reduction reaction sites are transferred to cadmium zinc sulfide, and the problem that perovskite lacks reaction sites is solved. The method for synthesizing the heterojunction by in-situ growth through heat injection adopted by the invention ensures that the surface binding force of two substances is strong, and is more beneficial to charge transmission. The invention has the advantages of low price, strong applicability of the treatment method, popularization of technical lines and the like.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to preparation and photocatalysis application of a composite photocatalyst for constructing a perovskite quantum dot heterojunction.
Background
The rise in atmospheric carbon dioxide levels and the exhaustion of fossil fuel reserves have raised serious concerns about the subsequent impact of global climate and future energy supply. The solar energy with rich and clean reserves is utilized to convert the carbon dioxide into the fuel such as methane or methanol, so that the two problems can be solved simultaneously, and a convenient energy storage means is provided. Photocatalytic carbon dioxide reduction is therefore considered one of the most promising technological means at present.
The lead halide perovskite quantum dot is considered as a substance with great development prospect in the field of photocatalysis due to the excellent performances of wide visible light region absorption, adjustable band gap, long carrier diffusion distance, low exciton binding energy, strong defect tolerance and the like. However, the disadvantages of serious carrier recombination, lack of carbon dioxide reduction reaction sites and the like also affect the photocatalytic performance inevitably. In order to solve the problems, a stable sulfide semiconductor is selected, namely, the cadmium zinc sulfur nanorod used in the invention and cesium lead bromine perovskite quantum dots construct a heterojunction, and a photocatalytic active site is transferred to the surface of cadmium zinc sulfur with stronger stability, so that the space separation of photo-generated electrons and holes is realized, and the transfer of the photo-generated electrons to the surface of a catalyst to participate in reduction reaction is facilitated. And, the mode of in-situ growth which can construct a tighter surface is selected on the synthesis of the compound, so that the compound has stronger charge transmission capability.
Therefore, we propose a preparation method of a composite photocatalyst for constructing perovskite quantum dot-cadmium zinc sulfur nanorod heterojunction and a photocatalytic application thereof to solve the problems.
Disclosure of Invention
The invention provides preparation and application of a composite photocatalyst for constructing a perovskite quantum dot heterojunction, which have the beneficial effects of facilitating carbon dioxide adsorption and activation, further improving the photocatalytic carbon dioxide reduction reaction activity, and solving the problems that the defects of lack of carbon dioxide reduction reaction sites and the like in the prior art affect the photocatalytic performance.
The invention provides the following technical scheme: the preparation method of the cadmium zinc sulfur nanorod comprises the following steps:
s1, firstly mixing ethylenediamine EDA with deionized water, and then mixing cadmium acetate Cd (Ac) 2 Zinc acetate Zn (Ac) 2 Adding the mixture with thioacetamide TAA into a mixed solution of ethylenediamine EDA and deionized water for hydrothermal reaction to obtain a mixed solution A;
s2, centrifugally separating the solution A, and drying the obtained precipitate product for 8 hours by a baking oven at 80 ℃ to obtain the cadmium zinc sulfur nanorod Cd 0.9 Zn 0.1 S powder.
As an alternative scheme of the preparation method of the cadmium zinc sulfur nano rod, the preparation method comprises the following steps: the hydrothermal reaction conditions in S1 are:
and (3) mixing and stirring by adopting a high-pressure reaction kettle, and after stirring uniformly, setting the temperature to react for 24 hours at 220 ℃ to obtain a mixed solution A.
As an alternative scheme of the preparation method of the cadmium zinc sulfur nano rod, the preparation method comprises the following steps: and S2, a washing step is further included, wherein the washing step is specifically that after the non-separation solution A is centrifuged, the obtained yellow precipitate is repeatedly washed for a plurality of times by using a deionized water and ethanol mixed solution, and then the yellow precipitate is dried.
As the inventionAn alternative scheme of the preparation method of the cadmium zinc sulfur nanorod is that: cadmium acetate Cd (Ac) in the mixed solution A 2 Zinc acetate Zn (Ac) 2 The ratio of thioacetamide TAA, ethylenediamine EDA to deionized water was 18mol:2mol:25mol:30L:30L.
Cesium lead bromine quantum dots and cadmium zinc sulfur nanorod composite photocatalyst prepared by adopting preparation method of cadmium zinc sulfur nanorod are prepared by adopting method of preparing cesium lead bromine quantum dots CsPbBr 3 QDs is loaded on Cd-Zn-S nanorod Cd 0.9 Zn 0.1 On S NRs, csPbBr is obtained 3 -Cd 0.9 Zn 0.1 S composite photocatalyst, comprising the following steps:
t1, taking cadmium zinc sulfur Cd 0.9 Zn 0.1 S powder, and lead bromide PbBr 2 Putting octadeceneode, oleic acid OA and oleylamine OAm into a three-necked flask together, and heating to 150 ℃ to obtain a solution B;
t2, another three-necked flask was charged with cesium source Cs 2 CO 3 Simultaneously adding octadeceneode and oleic acid OA, and heating to 150 ℃ under argon atmosphere to obtain cesium source solution C;
t3, adding cesium source solution C into solution B obtained by T1, reacting for 5 seconds at high temperature, immediately placing into ice water bath, cooling to room temperature, washing, centrifuging, purifying, and drying to obtain CsPbBr 3 -Cd 0.9 Zn 0.1 S composite photocatalyst.
As an alternative scheme of the method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by the preparation method of the cadmium zinc sulfur nanorod, provided by the invention, the method comprises the following steps: cadmium zinc sulfur Cd in the mixed solution B 0.9 Zn 0.1 S powder, lead bromide PbBr 2 The ratio of octadeceneode, oleic acid OA, oleylamine OAm was 1.25kg:9.4mol:250L:50L:25L.
As an alternative scheme of the method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by the preparation method of the cadmium zinc sulfur nanorod, provided by the invention, the method comprises the following steps: cesium carbonate Cs in the mixed solution C 2 CO 3 The ratio of octadeceneode to oleic acid OA was 1.15mol:19L:1.14L.
As an alternative scheme of the method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by the preparation method of the cadmium zinc sulfur nanorod, provided by the invention, the method comprises the following steps: cesium carbonate Cs participating in the reaction in T3 2 CO 3 And lead bromide PbBr 2 The ratio of (2) is 1mol:8.17mol.
A photocatalytic carbon dioxide reduction method, which adopts the product obtained by the preparation method of the cadmium zinc sulfur nanorod according to any one of claims 1-4 and the preparation method of the cesium lead bromine perovskite quantum dot and cadmium zinc sulfur nanorod composite photocatalyst according to any one of claims 5-8.
The invention has the following beneficial effects:
1. the invention adopts a method of thermal injection in-situ growth to prepare CsPbBr which can efficiently separate photo-generated electron-hole pairs and has stronger interfacial charge transmission capability 3 -Cd 0.9 Zn 0.1 S composite photocatalyst. Cesium lead bromine quantum dot (CsPbBr) 3 QDs) to cadmium zinc sulfur nanorods (Cd) 0.9 Zn 0.1 S NRs) to effectively inhibit cesium lead bromine quantum dots (CsPbBr) 3 QDs).
2. The preparation and the photocatalysis application of the composite photocatalyst for constructing the perovskite quantum dot heterojunction are that after the heterojunction is successfully constructed, catalytic reaction sites are transferred to cadmium zinc sulfur nanorods with rich active sites, so that the photocatalytic carbon dioxide reduction reaction is facilitated.
3. The preparation method of the composite photocatalyst for constructing the perovskite quantum dot heterojunction and the photocatalytic application thereof, and the preparation method of the thermal injection in-situ growth are beneficial to constructing a more tightly contacted surface, and reduce the cesium lead bromine quantum dot (CsPbBr) 3 QDs) and cadmium zinc sulfur nanorods (Cd) 0.9 Zn 0.1 S NRs), enhancing the interface charge transport capability of the heterojunction.
Drawings
FIG. 1 is a schematic diagram of the present invention CsPbBr 3 Is the synthesis of Cd 0.9 Zn 0.1 Preparation of S and CsPbBr 3 -Cd 0.9 Zn 0.1 Schematic preparation of S complexes.
FIG. 2 is CsPbBr 3 、Cd 0.9 Zn 0.1 S and CsPbBr 3 -Cd 0.9 Zn 0.1 Transmission Electron Microscope (TEM) images of the S complex are intended.
FIG. 3 shows CsPbBr prepared according to the invention 3 -Cd 0.9 Zn 0.1 S complex and CsPbBr 3 Fluorescence intensity map of quantum dot and CsPbBr 3 Quantum dots, cd 0.9 Zn 0.1 S and CsPbBr 3 -Cd 0.9 Zn 0.1 Photocurrent response plot of S-complex.
FIG. 4 is a CsPbBr of the present invention 3 Quantum dots, cd 0.9 Zn 0.1 S and CsPbBr 3 -Cd 0.9 Zn 0.1 The activity results of the S complex photocatalytic carbon dioxide reduction are shown.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The rise in atmospheric carbon dioxide levels and the exhaustion of fossil fuel reserves have raised serious concerns about the subsequent impact of global climate and future energy supply. The solar energy with rich and clean reserves is utilized to convert the carbon dioxide into the fuel such as methane or methanol, so that the two problems can be solved simultaneously, and a convenient energy storage means is provided. Photocatalytic carbon dioxide reduction is therefore considered one of the most promising technological means at present.
The lead halide perovskite quantum dot is considered as a substance with great development prospect in the field of photocatalysis due to the excellent performances of wide visible light region absorption, adjustable band gap, long carrier diffusion distance, low exciton binding energy, strong defect tolerance and the like. However, the disadvantages of serious carrier recombination, lack of carbon dioxide reduction reaction sites and the like also affect the photocatalytic performance inevitably. In order to solve the problems, a stable sulfide semiconductor is selected, namely, the cadmium zinc sulfur nanorod used in the invention and cesium lead bromine perovskite quantum dots construct a heterojunction, and a photocatalytic active site is transferred to the surface of cadmium zinc sulfur with stronger stability, so that the space separation of photo-generated electrons and holes is realized, and the transfer of the photo-generated electrons to the surface of a catalyst to participate in reduction reaction is facilitated. And, the mode of in-situ growth which can construct a tighter surface is selected on the synthesis of the compound, so that the compound has stronger charge transmission capability.
Therefore, we propose a preparation method of a composite photocatalyst for constructing perovskite quantum dot-cadmium zinc sulfur nanorod heterojunction and a photocatalytic application thereof to solve the problems.
Aiming at the problems existing in the prior art, the invention aims to provide a preparation and application of a composite photocatalyst for constructing a perovskite quantum dot heterojunction. The construction of the heterojunction of cesium lead bromine quantum dots (CsPbBr 3 QDs) -cadmium zinc sulfur nanorods (Cd0.9Zn0.1S NRs) is beneficial to the space separation of photo-generated electrons and holes, so that more photo-generated electrons can participate in the reduction reaction on the surface of the catalyst, and meanwhile, the cadmium zinc sulfur nanorods provide more active sites for the reduction of photocatalytic carbon dioxide, are beneficial to the adsorption and activation of carbon dioxide, and further improve the reduction reaction activity of the photocatalytic carbon dioxide. The method has the advantages of low price, strong applicability of the treatment method, popularization of technical lines and the like.
In order to solve the problems, the invention provides the following technical scheme: referring to fig. 1-4, a method for preparing a cadmium zinc sulfur nanorod includes the following steps:
s1, firstly mixing Ethylenediamine (EDA) with deionized water, and then adding cadmium acetate (Cd (Ac) 2), zinc acetate (Zn (Ac) 2) and Thioacetamide (TAA) into a mixed solution of Ethylenediamine (EDA) and deionized water for hydrothermal reaction to obtain a mixed solution A;
the hydrothermal reaction conditions in S1 are:
and (3) mixing and stirring by adopting a high-pressure reaction kettle, and after stirring uniformly, setting the temperature to react for 24 hours at 220 ℃ to obtain a mixed solution A.
S2, centrifugally separating the solution A, and drying the obtained precipitate product by an oven at 80 ℃ for 8 hours to obtain cadmium zinc sulfur nanorod (Cd0.9Zn0.1S) powder.
Wherein: and S2, a washing step is further included, wherein the washing step is specifically that after the non-separation solution A is centrifuged, the obtained yellow precipitate is repeatedly washed for a plurality of times by using a deionized water and ethanol mixed solution, and then the yellow precipitate is dried.
Wherein: the ratio of cadmium acetate (Cd (Ac) 2), zinc acetate (Zn (Ac) 2), thioacetamide (TAA), ethylenediamine (EDA) to deionized water in the mixed solution A is 18mol:2mol:25mol:30L:30L.
The method for preparing the cesium lead bromine quantum dots and the cadmium zinc sulfur nanorod composite photocatalyst by adopting the preparation method of the cadmium zinc sulfur nanorod loads the cesium lead bromine quantum dots (CsPbBr 3 QDs) on the cadmium zinc sulfur nanorod (Cd0.9Zn0.1S NRs) to obtain the (CsPbBr 3-Cd0.9Zn0.1S) composite photocatalyst, and comprises the following steps of:
t1, taking cadmium zinc sulfide (Cd0.9Zn0.1S) powder, putting the powder into a three-necked flask together with lead bromide (PbBr 2), octadecene (ODE), oleic Acid (OA) and oleylamine (OAm), and heating to 150 ℃ to obtain a solution B;
t2, adding cesium source substance Cs2CO3 into another three-neck flask, simultaneously adding Octadecene (ODE) and Oleic Acid (OA), and heating to 150 ℃ under argon atmosphere to obtain cesium source solution C;
and T3, adding cesium source solution C into solution B obtained by T1, reacting for 5 seconds at high temperature, immediately putting into ice water bath, cooling to room temperature, washing, centrifuging, purifying and drying to obtain the CsPbBr3-Cd0.9Zn0.1S composite photocatalyst.
Wherein: the ratio of cadmium zinc sulfide (Cd0.9Zn0.1S) powder, lead bromide (PbBr 2), octadecene (ODE), oleic Acid (OA) and oleylamine (OAm) in the mixed solution B is 1.25kg:9.4mol:250L:50L:25L.
Wherein: the proportion of cesium carbonate (Cs 2CO 3), octadecene (ODE) and Oleic Acid (OA) in the mixed solution C is 1.15mol:19L:1.14L.
Wherein: the ratio of cesium carbonate (Cs 2CO 3) to lead bromide (PbBr 2) in the T3 to participate in the reaction is 1mol:8.17mol.
Constructing an application of the perovskite quantum dot-cadmium zinc sulfur nanorod composite photocatalyst, and applying the product obtained by the method to the field of photocatalytic carbon dioxide reduction;
the principle of the preparation method is as follows: the preparation of the composite photocatalyst adopts an in-situ growth mode, specifically, the prepared cadmium zinc sulfur nanorod (Cd0.9Zn0.1S NRs) powder is put into a precursor solution for preparing cesium lead bromine, the cesium lead bromine quantum dots (CsPbBr 3 QDs) are in-situ grown on the cadmium zinc sulfur nanorod through a thermal injection mode, and the composite photocatalyst of cesium lead bromine and cadmium zinc sulfur (CsPbBr 3-Cd0.9Zn0.1S) is finally obtained after centrifugation, washing and drying.
The combination of cesium lead bromine and cadmium zinc sulfur improves the serious problem of carrier combination of perovskite per se to a certain extent, promotes the separation of electron-hole pairs of perovskite, and is favorable for the reduction reaction of photogenerated electrons transmitted to the surface of the catalyst. In addition, by constructing a heterojunction, carbon dioxide reduction reaction sites are transferred to cadmium zinc sulfide, and the problem that perovskite lacks reaction sites is solved.
The method for synthesizing the heterojunction by in-situ growth through heat injection adopted by the invention ensures that the surface binding force of two substances is stronger and the method is more beneficial to charge transmission. The method has the advantages of low price, strong applicability of the treatment method, popularization of technical lines and the like.
When in use, the invention adopts a method of thermal injection in-situ growth to prepare
CsPbBr3-Cd0.9Zn0.1S composite photocatalyst.
As shown in a Transmission Electron Microscope (TEM) diagram in FIG. 2, cesium lead bromine quantum dots (CsPbBr 3 QDs) are closely attached to cadmium zinc sulfur nanorods (Cd0.9Zn0.1S NRs), and the CsPbBr3-Cd0.9Zn0.1S heterojunction is successfully constructed.
As shown in fig. 3, after being compounded with cadmium zinc sulfur nanorods (cd0.9zn0.1s NRs), the fluorescence intensity of cesium lead bromine quantum dots (CsPbBr 3 QDs) appears to be significantly quenched, and the compound shows stronger photocurrent response, indicating efficient carrier separation and interfacial charge transport capability between CsPbBr3 and cd0.9zn0.1s due to excellent contact interface.
In addition, as shown in fig. 4, the CsPbBr3-cd0.9zn0.1s composite photocatalyst shows a significant improvement in the ability to photocatalytic carbon dioxide. The method has the advantages of low price, strong applicability of the treatment method, popularization of technical lines and the like.
A photocatalytic carbon dioxide reduction method, which adopts the product obtained by the preparation method of the cadmium zinc sulfur nanorod according to any one of claims 1-4 and the preparation method of the cesium lead bromine perovskite quantum dot and cadmium zinc sulfur nanorod composite photocatalyst according to any one of claims 5-8.
The above description is only of the preferred embodiments of the present invention; the scope of the invention is not limited in this respect. Any person skilled in the art, within the technical scope of the present disclosure, may apply to the present invention, and the technical solution and the improvement thereof are all covered by the protection scope of the present invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (9)
1. A preparation method of a cadmium zinc sulfur nano rod is characterized by comprising the following steps: the method comprises the following steps:
s1, firstly mixing ethylenediamine EDA with deionized water, and then mixing cadmium acetate Cd (Ac) 2 Zinc acetate Zn (Ac) 2 Adding the mixture with thioacetamide TAA into a mixed solution of ethylenediamine EDA and deionized water for hydrothermal reaction to obtain a mixed solution A;
s2, centrifugally separating the solution A, and drying the obtained precipitate product for 8 hours by a baking oven at 80 ℃ to obtain the cadmium zinc sulfur nanorod Cd 0.9 Zn 0.1 S powder.
2. The method for preparing the cadmium zinc sulfur nanorod according to claim 1, which is characterized in that: the hydrothermal reaction conditions in S1 are:
and (3) mixing and stirring by adopting a high-pressure reaction kettle, and after stirring uniformly, setting the temperature to react for 24 hours at 220 ℃ to obtain a mixed solution A.
3. The method for preparing the cadmium zinc sulfur nanorod according to claim 1, which is characterized in that: and S2, a washing step is further included, wherein the washing step is specifically that after the non-separation solution A is centrifuged, the obtained yellow precipitate is repeatedly washed for a plurality of times by using a deionized water and ethanol mixed solution, and then the yellow precipitate is dried.
4. The method for preparing the cadmium zinc sulfur nanorod according to claim 1, which is characterized in that: cadmium acetate Cd (Ac) in the mixed solution A 2 Zinc acetate Zn (Ac) 2 The ratio of thioacetamide TAA, ethylenediamine EDA to deionized water was 18mol:2mol:25mol:30L:30L.
5. A method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by adopting the preparation method of the cadmium zinc sulfur nanorod disclosed in claim 1 is characterized by comprising the following steps: cesium lead bromine quantum dot CsPbBr 3 QDs loading to cadmium zinc sodium sulfideRice stick Cd 0.9 Zn 0.1 On S NRs, csPbBr is obtained 3 -Cd 0.9 Zn 0.1 S composite photocatalyst, comprising the following steps:
t1, taking cadmium zinc sulfur Cd 0.9 Zn 0.1 S powder, and lead bromide PbBr 2 Putting octadeceneode, oleic acid OA and oleylamine OAm into a three-necked flask together, and heating to 150 ℃ to obtain a solution B;
t2, another three-necked flask was charged with cesium source Cs 2 CO 3 Simultaneously adding octadeceneode and oleic acid OA, and heating to 150 ℃ under argon atmosphere to obtain cesium source solution C;
t3, adding cesium source solution C into solution B obtained by T1, reacting for 5 seconds at high temperature, immediately placing into ice water bath, cooling to room temperature, washing, centrifuging, purifying, and drying to obtain CsPbBr 3 -Cd 0.9 Zn 0.1 S composite photocatalyst.
6. The method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by using the preparation method of the cadmium zinc sulfur nanorod according to claim 5 is characterized by comprising the following steps: cadmium zinc sulfur Cd in the mixed solution B 0.9 Zn 0.1 S powder, lead bromide PbBr 2 The ratio of octadeceneode, oleic acid OA, oleylamine OAm was 1.25kg:9.4mol:250L:50L:25L.
7. The method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by using the preparation method of the cadmium zinc sulfur nanorod according to claim 5 is characterized by comprising the following steps: cesium carbonate Cs in the mixed solution C 2 CO 3 The ratio of octadeceneode to oleic acid OA was 1.15mol:19L:1.14L.
8. The method for preparing the cesium lead bromine quantum dot and cadmium zinc sulfur nanorod composite photocatalyst by using the preparation method of the cadmium zinc sulfur nanorod according to claim 5 is characterized by comprising the following steps: cesium carbonate Cs participating in the reaction in T3 2 CO 3 And lead bromide PbBr 2 The ratio of (2) is 1mol:8.17mol.
9. A photocatalytic carbon dioxide reduction method, characterized by: the photocatalytic carbon dioxide reduction method adopts a preparation method of the cadmium zinc sulfur nanorod according to any one of claims 1-4 and a product obtained by a preparation method of the cesium lead bromine quantum dot and the cadmium zinc sulfur nanorod composite photocatalyst prepared by a preparation method of the cadmium zinc sulfur nanorod according to any one of claims 5-8.
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