CN113856713B - For CO 2 Lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst for photocatalytic reduction and preparation method and application thereof - Google Patents

For CO 2 Lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst for photocatalytic reduction and preparation method and application thereof Download PDF

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CN113856713B
CN113856713B CN202111130759.8A CN202111130759A CN113856713B CN 113856713 B CN113856713 B CN 113856713B CN 202111130759 A CN202111130759 A CN 202111130759A CN 113856713 B CN113856713 B CN 113856713B
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CN113856713A (en
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刘曰利
周敏
陈文�
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Wuhan University of Technology WUT
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Abstract

For CO 2 Reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst, wherein the lead-free double perovskite quantum dot and the two-dimensional material are compounded to form a heterojunction structure, and the chemical general formula of the lead-free double perovskite quantum dot is Cs 2 B Ⅰ B Ⅱ X 6 Wherein B is Ⅰ Selected from Ag + ，In + ，Cu + Any one of ions, B Ⅱ Selected from In 3+ ，Bi 3+ ，Sb 3+ X is selected from Cl ‑ ，Br ‑ ，I ‑ Any one ion of the two-dimensional material is selected from Ti 3 C 2 Bismuth alkene, black phosphorus. The preparation method comprises the following steps: dissolving two-dimensional material in octadecene, ultrasonic dispersing, and placing in Cs 2 CO 3 ，B Ⅰ OAc，B Ⅱ (OAc) 3 And (3) heating, injecting a mixed solution of trimethyl halosilane and hydrochloric acid, reacting, cooling, washing and drying to obtain the composite photocatalyst. Through CO 2 Photocatalytic reduction test of the resulting CO 2 The reduction products are mainly CO and CH 4 The yield is obviously improved; the photocatalytic cycle test shows no obvious change in yield, indicating excellent CO 2 Photocatalytic reduction stability.

Description

For CO 2 Lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst for photocatalytic reduction and preparation method and application thereof
Technical Field
The invention relates to a photocatalyst, a preparation method and the application technical field thereof, in particular to a catalyst for CO 2 A preparation method of a reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst.
Background
In the form of CO 2 Excessive emissions of major greenhouse gases cause global warming and an accompanying series of extreme weather, severely affecting the survival of future human civilization. Under the current situation, how to convert CO under the condition that the structure of the stored energy is not changed greatly 2 Efficient collection of transformations and utilization is a current research hotspot. The photocatalysis technology is used for reducing CO by using clean energy solar energy as drive 2 CO reduction 2 Hydrocarbon fuel is obtained while discharging. CO 2 The photocatalytic reduction reaction has the following advantages: reduction of the product to CH 4 、CO、H 2 A hydrocarbon fuel; the reaction process is driven by clean and renewable energy sources-solar energy, so that secondary pollution to the environment in the process of catalyzing and degrading carbon dioxide is avoided; the reaction device of the reaction is simple, the reaction conditions are easy to reach (room temperature and atmospheric pressure), and the like, and the method is considered to be an effective mode for solving the global warming and energy crisis. Heretofore, it has been developedResearchers have been reducing CO by photocatalysis 2 A great deal of application research is carried out, and the preparation of a high-efficiency photocatalyst is particularly important.
Quantum dots, which are used as zero-dimensional nano semiconductor materials, have attracted great interest to researchers because of their numerous excellent physical properties, such as quantum size effects, multi-exciton excitation effects, and ultrafast exciton conduction. Leadless double perovskite quantum dot (CsB) Ⅰ B Ⅱ The X) solves the problems of unfriendly environment, poor stability and the like of the lead-based perovskite quantum dot, and the synthesis process is mature day by day. But its wide band gap, rich surface ligands, have limited their application in the field of photocatalysis.
Factors affecting the performance of the composite photocatalyst mainly include the following aspects: crystal structure, band structure, crystal size, etc. Wherein the particle size of the photocatalyst is closely related to the size of the specific surface area, and in the photocatalytic reaction, the number of the redox reaction sites of the photocatalytic material is directly determined by the specific surface area. The two-dimensional material is a typical material with large specific surface area, has the advantages of multiple surface active sites, abundant host-guest selectivity, high electron separation efficiency and the like, and can be used as a substrate material to load quantum dots. However, most two-dimensional materials have the defects of instability, easy recombination of photo-generated electrons and holes, and the like, so researchers compound the two-dimensional materials with other semiconductor materials to form a heterojunction structure so as to reduce the recombination of the photo-generated electrons and the holes and improve the photocatalytic performance. Semiconductor heterojunction is divided into three categories:
type I: the valence band of the semiconductor 1 is positive to the valence band of the semiconductor 2, the conduction band of the semiconductor 1 is negative to the conduction band of the semiconductor 2, and photo-generated electrons-holes migrate from the semiconductor 1 to the semiconductor 2, so that the light absorption range can be effectively prolonged, and the light utilization rate can be increased;
type II: the valence band of the semiconductor 2 is positive to the valence band of the semiconductor 1, the conduction band of the semiconductor 1 is negative to the conduction band of the semiconductor 2, the photo-generated electrons are transferred from the conduction band of the semiconductor 1 to the conduction band of the semiconductor 2, and the photo-generated holes are transferred from the valence band of the semiconductor 2 to the valence band of the semiconductor 1, so that the recombination of photo-generated electron-hole pairs can be effectively reduced, and the photo-catalytic reaction efficiency is improved.
Disclosure of Invention
It is an object of the present invention to provide a method for CO 2 The reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst has a semiconductor heterojunction structure composed of different band gap structures, can prolong the light absorption range of the catalyst, enhance the migration efficiency of internal carriers, reduce the recombination of photo-generated electron-hole pairs, and has high stability and high-efficiency photocatalytic performance.
It is a further object of the invention to provide a method for CO 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst can realize band gap adjustment, and is simple in process, good in reproducibility and environment-friendly.
It is a further object of the invention to provide a method for CO 2 The application of the reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst.
One of the solutions adopted for achieving the purpose of the invention is as follows:
for CO 2 Reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst, wherein the lead-free double perovskite quantum dot and the two-dimensional material are compounded to form a heterojunction structure, and the chemical general formula of the lead-free double perovskite quantum dot is Cs 2 B Ⅰ B Ⅱ X 6 Wherein B is Ⅰ Selected from Ag + ，In + ，Cu + Any one of ions, B Ⅱ Selected from In 3+ ，Bi 3+ ，Sb 3+ X is selected from Cl - ，Br - ，I - Any one ion of the two-dimensional material is selected from Ti 3 C 2 Bismuth alkene, black phosphorus.
Selecting different B Ⅰ Or B is a Ⅱ The metal, lead-free double perovskite quantum dots can have different band gap sizes, valence bands and conduction band positions.
In the technical scheme, the leadless double perovskite quantum dot @ two-dimensional material composite photocatalyst has an I-type heterojunction structure or a II-type heterojunction structure or an S-type heterojunction structure or a Z-type heterojunction structure.
In the technical scheme, the lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst comprises CO 2 The photocatalytic reduction product is carbon monoxide (CO) or methane (CH) 4 ) Or formic acid (HCOOH).
The scheme adopted for realizing the second purpose of the invention is as follows:
for CO 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst comprises the following steps:
step 1. Cs is processed 2 CO 3 ，B Ⅰ OAc，B Ⅱ (OAc) 3 Dissolving in octadecene, heating and mixing uniformly under the protection of inert gas;
step 2, dissolving a two-dimensional material in octadecene, dispersing, adding the dispersed material into the product obtained in the step 1, uniformly mixing, adding oleic acid and oleic acid ligand, and preserving heat until the reaction is complete to obtain a mixed solution;
step 3, heating the mixed solution obtained in the step 2, adding a mixed solution of trimethyl halosilane and hydrochloric acid, and cooling after the reaction is completed;
and 4, centrifuging, washing, drying and grinding the product obtained in the step 3 to obtain the lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst.
In the above technical solution, cs is in step 1, step 2 and step 3 2 CO 3 、B Ⅰ OAc、B Ⅱ (OAc) 3 The ratio of oleic acid, oleic acid ligand, trimethylhalosilane and hydrochloric acid is 0.1-1mmol:0.2-0.5mmol:0.5-1mmol:30-60mg:1-3mL:1-3mL:1-2mL:0.3-0.7mL.
In the above technical solution, in step 1, B Ⅰ OAc is any one of AgOAc, inOAc, cuOAc, B Ⅱ (OAc) 3 For In (OAc) 3 ，Bi(OAc) 3 ，Sb(OAc) 3 The inert gas is argon or nitrogen, and the temperature is 100-120 ℃.
In the above technical solution, in step 2, the two-dimensional material is Ti 3 C 2 Any one of bismuth alkene and black phosphorus, and the heat preservation temperature is 100-120 DEG C。
In the technical scheme, in the step 3, the temperature is raised to 170-190 ℃ and the reaction time is 100-200s; in the step 4, the tertiary butanol solution and the normal hexane solution are adopted for alternate washing, the centrifugation time is 3-7min, the rotating speed is 7000-10000rpm, and the grinding is carried out until no obvious particles exist.
The scheme adopted for achieving the third purpose of the invention is as follows:
according to the above for CO 2 Reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst or CO prepared by the preparation method 2 Reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst for high-efficiency photocatalytic reduction of CO 2 Is used in the field of applications.
The beneficial effects of the invention are as follows:
1. for CO 2 The reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst takes the zero-dimensional quantum dot@two-dimensional material as the photocatalyst, has excellent photo-generated electron hole separation and transfer capacity, has inhibition effect on the recombination of photo-generated electrons and holes, and has adjustable light absorption performance. The strong interaction between the zero-dimensional quantum dots and the two-dimensional material can play a good role in dispersion and stabilization, an interface is formed between the zero-dimensional quantum dots and the two-dimensional material, and the surface interface of the material is modified, so that the advantages of wide adjustability of band gaps, high light absorption cutting edge, strong quantum confinement effect and the like are shown, and for the lead-free double perovskite quantum dots, the size of energy bands is changed by utilizing different transition metal double metal systems, and the valence band and conduction band positions of the quantum dots are adjusted. Meanwhile, two-dimensional materials with different band gap structures and quantum dots are selected to be composited to construct different heterojunction structures as photocatalysts for CO 2 And performing photocatalytic reduction to obtain the composite photocatalytic material with high stability and high efficiency. Compared with lead-based perovskite, the lead-free double perovskite quantum dot is free of lead, toxic and environment-friendly.
2. For CO 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst is simple to operate, and the synthesis method is simple and efficient, good in reproducibility and environment-friendly.
3. For CO 2 The reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst can be widely applied to photocatalytic reduction of CO 2 ，CO 2 The photocatalytic reduction efficiency is obviously improved, and the photocatalytic stability is also enhanced to a certain extent.
Drawings
FIG. 1 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti prepared in comparative example 2 3 C 2 XRD pattern of nanoplatelets.
FIG. 2 is a diagram of Ti prepared in comparative example 1 according to the present invention 3 C 2 Nanoplatelets, cs prepared in example 1 2 AgInCl 6 Quantum dot @ Ti 3 C 2 SEM image of composite photocatalyst, wherein FIG. 2 (a) is Ti 3 C 2 Nanosheet SEM image, FIG. 2 (b) is Cs 2 AgInCl 6 Quantum dot @ Ti 3 C 2 SEM image of the composite photocatalyst.
FIG. 3 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti prepared in comparative example 2 3 C 2 The ultraviolet-visible characterization result of the nano-sheet.
FIG. 4 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti prepared in comparative example 2 3 C 2 CO of nanoplatelets 2 A photocatalytic reduction performance graph, wherein FIG. 4 (a) shows the performance curve of the reduction product as CO and FIG. 4 (b) shows the reduction product as CH 4 Performance curves fig. 4 (c) is a photocatalytic cycle stability test curve.
FIG. 5 shows Cs prepared in example 2 of the present invention 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst and Cs prepared in comparative example 3 2 AgBiI 6 The result of the morphological microstructure characterization of the quantum dots, wherein FIG. 5 (a) is Cs 2 AgBiI 6 Quantum dot TEM image, FIG. 5 (b) is Cs 2 AgBiI 6 Quantum dot HRTEM image, FIG. 5 (c) is Cs 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst TEM image.
FIG. 6 shows Cs prepared in example 3 2 AgInBr 6 And (3) a morphology characterization result of the quantum dot@bismuth alkene composite photocatalyst. FIG. 6 (a) is Cs 2 AgInBr 6 TEM image of Quantum dot @ bismuth alkene composite photocatalyst, FIG. 6 (b) is Cs 2 AgInBr 6 HRTEM image of quantum dot @ bismuth alkene composite photocatalyst.
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.
Example 1
Cs 2 AgInCl 6 Quantum dot @ Ti 3 C 2 The preparation method of the composite photocatalyst comprises the following steps:
step 1. Mixing 0.4mmol Cs 2 CO 3 ，0.3mmol AgOAc，0.6mmol In(OAc) 3 Dissolving in 20mL of octadecene, placing in a 50mL three-necked flask, heating to 100 ℃ under the protection of argon, and continuously stirring until the mixture is uniformly mixed;
step 2. 50mg of Ti 3 C 2 Dissolving in 5mL of octadecene, performing ultrasonic dispersion for 30min, adding the solution into an triangular flask where the product obtained in the step 1 is located, continuously stirring, wherein the ultrasonic power is 800W, the stirring time is 15min, then adding 2mL of oleic acid and 2.5mL of oleylamine ligand, and performing heat preservation for 1h at 100 ℃ to obtain a mixed solution;
step 3, heating the mixed solution obtained in the step 2 to 170 ℃, quickly adding 1mL of mixed solution of trimethylhalosilane and 0.3mL of hydrochloric acid, reacting for 100 seconds, and cooling;
step 4, adding the product obtained in the step 3 into 30mL of tertiary butanol solution for separationWashing heart for 5min at 10000rpm, adding the precipitate into 10mL of n-hexane solution, centrifuging for 3min at 8000rpm, repeatedly washing for 2 times, vacuum drying, and grinding for 10min until no obvious particles exist to obtain Cs 2 AgInCl 6 Quantum dot @ Ti 3 C 2 A composite photocatalyst.
Example 2
Cs 2 AgBiI 6 The preparation method of the quantum dot@black phosphorus composite photocatalyst comprises the following steps:
step 1. Mixing 0.4mmol Cs 2 CO 3 ，0.4mmol AgOAc，0.8mmol Bi(OAc) 3 Dissolving in 20mL of octadecene, placing in a 50mL three-necked flask, heating to 100 ℃ under the protection of argon, and continuously stirring until the mixture is uniformly mixed;
step 2, dissolving 60mg of black phosphorus in 5mL of octadecene, adding the solution into an triangular flask where the product obtained in the step 1 is located after ultrasonic dispersion for 30min, continuously stirring, wherein the ultrasonic power is 800W, the stirring time is 15min, then adding 3mL of oleic acid and 3mL of oleylamine ligand, and carrying out heat preservation at 110 ℃ for 1h to obtain a mixed solution;
step 3, heating the mixed solution obtained in the step 2 to 180 ℃, quickly adding 1.2mL of mixed solution of trimethyliodosilane and 0.4mL of hydrochloric acid, reacting for 150 seconds, and cooling;
step 4, adding the product obtained in the step 3 into 30mL of tertiary butanol solution for centrifugal washing, wherein the centrifugal time is 5min, the centrifugal rotating speed is 10000rpm, then adding the precipitate into 10mL of normal hexane solution for centrifugal washing, the centrifugal time is 3min, the centrifugal rotating speed is 8000rpm, repeatedly washing for 2 times, taking the precipitate, vacuum drying, grinding for 10min until no obvious particles exist, and obtaining Cs 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst.
Wherein, black phosphorus is purchased from Jiangsu Xianfeng nano materials science and technology Co.
Example 3
Cs 2 AgInBr 6 The preparation method of the quantum dot@bismuth alkene composite photocatalyst comprises the following steps:
step 1. Mixing 0.4mmol Cs 2 CO 3 ，0.3mmol AgOAc，0.6mmol Bi(OAc) 3 Dissolving in 20mL of octadecene, placing in a 50mL three-necked flask, heating to 120 ℃ under the protection of argon, and continuously stirring until the mixture is uniformly mixed;
step 2, dissolving 50mg of bismuth alkene in 5mL of octadecene, adding the solution into an triangular flask where the product obtained in the step 1 is located after ultrasonic dispersion for 30min, continuously stirring, wherein the ultrasonic power is 800W, the stirring time is 20min, then adding 3mL of oleylamine and 3mL of oleic acid ligand, and carrying out heat preservation at 120 ℃ for 1h to obtain a mixed solution;
step 3, heating the mixed solution obtained in the step 2 to 170 ℃, quickly adding 1mL of mixed solution of trimethyl bromosilane and 0.3mL of hydrochloric acid, reacting for 180 seconds, and cooling;
step 4, adding the product obtained in the step 3 into 30mL of tertiary butanol solution for centrifugal washing, wherein the centrifugal time is 5min, the centrifugal rotating speed is 10000rpm, then adding the precipitate into 10mL of normal hexane solution for centrifugal washing, the centrifugal time is 3min, the centrifugal rotating speed is 8000rpm, repeatedly washing for 2 times, taking the precipitate, vacuum drying, grinding for 10min until no obvious particles exist, and obtaining Cs 2 AgInBr 6 Quantum dot @ bismuth alkene composite photocatalyst.
Comparative example 1
Cs 2 AgInCl 6 The preparation method of the quantum dot comprises the following steps:
step A1 taking 0.4mmol Cs 2 CO 3 ，0.3mmol AgOAc，0.6mmol In(OAc) 3 Dissolving in 20mL of octadecene, placing in a 50mL three-necked flask, heating to 100 ℃ under the protection of argon, continuously stirring until the mixture is uniform, adding 2mL of oleic acid and 2.5mL of oleylamine ligand, and preserving the temperature for 1h at 100 ℃ to obtain a mixed solution;
a2, heating the mixed solution obtained in the step 1 to 170 ℃, quickly adding 1mL of mixed solution of trimethylhalosilane and 0.3mL of hydrochloric acid, reacting for 100 seconds, and cooling;
step A3, adding the product obtained in the step 2 into 30mL of tertiary butanol solution for centrifugal washing, wherein the centrifugal time is 5min, the centrifugal speed is 10000rpm, adding the precipitate into 10mL of normal hexane solution for centrifugal washing, the centrifugal time is 3min, the centrifugal speed is 8000rpm, and repeating the stepsWashing for 2 times, and vacuum drying at 80 ℃ for 12 hours to obtain Cs 2 AgInCl 6 Quantum dots.
Comparative example 2
Ti 3 C 2 The preparation method of the nano-sheet comprises the following steps:
step B1. Weighing 300mgTi 3 AlC 2 The solution was stirred in HF solution for 7days and rinsed with deionized water to a solution ph=7.
And B2, carrying out ice bath ultrasonic stripping on the solution obtained in the step 1, wherein the ultrasonic power is 800W, and the ultrasonic time is 4 hours.
B3, centrifuging the solution obtained in the step 2 for 10min at 5000rpm, collecting supernatant, centrifuging the obtained supernatant at 13000rpm for 15min, collecting precipitate, and vacuum drying at room temperature for 24 hr to obtain Ti 3 C 2 A nano-sheet.
Comparative example 3
Cs 2 AgBiI 6 The preparation method of the quantum dot comprises the following steps:
step C1 taking 0.4mmol Cs 2 CO 3 ，0.3mmol AgOAc，0.6mmol Bi(OAc) 3 Dissolve in 20mL octadecene and place in 50mL three-necked flask, under argon protection, heat to 100deg.C, continue stirring until mixing well. Adding 3mL of oleic acid and 3mL of oleylamine ligand, and preserving heat for 1h at 100 ℃ to obtain a mixed solution;
step C2., heating the mixed solution obtained in the step 1 to 180 ℃, quickly adding 1.2mL of mixed solution of trimethyliodosilane and 0.4mL of hydrochloric acid, reacting for 120 seconds, and cooling;
step C3. adding the product obtained in step 2 into 30mL of tertiary butanol solution, centrifugally washing for 5min at 10000rpm, adding the precipitate into 10mL of normal hexane solution, centrifugally washing for 3min at 8000rpm, repeatedly washing for 2 times, and vacuum drying at 80deg.C for 12 hr to obtain Cs 2 AgBiI 6 Quantum dots.
FIG. 1 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti3C2 nano prepared in comparative example 2XRD pattern of rice flakes. As shown in the XRD pattern of FIG. 1, cs 2 AgInCl 6 Quantum dots and Ti 3 C 2 Obvious Cs can be observed after compounding 2 AgInCl 6 Quantum dots and Ti 3 C 2 Diffraction peaks of the nanoplatelets indicate that no significant phase change occurs before and after compounding.
FIG. 2 is a diagram of Ti prepared in comparative example 1 according to the present invention 3 C 2 Nanoplatelets (FIG. 2 a), cs prepared in example 1 2 AgInCl 6 Quantum dot @ Ti 3 C 2 SEM image of the composite photocatalyst (fig. 2 b). The composite photocatalyst prepared by the thermal injection method is still a two-dimensional sheet material, and compared with the composite photocatalyst before the composition, the morphology of the composite photocatalyst is not obviously changed.
FIG. 3 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti prepared in comparative example 2 3 C 2 The ultraviolet-visible characterization result of the nano-sheet. From this, it can be seen that Cs 2 AgInCl 6 The light absorption edge of the quantum dot is 340nm, ti 3 C 2 The nano-sheet has certain light absorption capacity in the visible light region, and Cs 2 AgInCl 6 Quantum dot @ Ti 3 C 2 The visible light region of the composite photocatalyst keeps certain light absorption capacity and is higher than pure Ti 3 C 2 A nano-sheet. Description when Ti is 3 C 2 Nanosheets and Cs 2 AgInCl 6 The light absorption capacity of the quantum dots after being compounded is improved.
FIG. 4 shows Cs prepared in example 1 of the present invention 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst and Cs prepared in comparative example 1 2 AgInCl 6 Quantum dots and Ti prepared in comparative example 2 3 C 2 CO of nanoplatelets 2 Photocatalytic reduction performance curve. Respectively weighing a certain amount of sample, dissolving in 20mL of ethyl acetate solution, and respectively charging saturated CO 2 The gas was tested under simulated solar conditions. Autonomously catalyzing reaction to 9h, and testing CO 2 The main products of the photocatalytic reduction are CO and CH 4 As shown in FIG. 4 (a) for CO performance curve and FIG. 4 (b) for CH4 performance curve for reduction product, cs 2 AgInCl 6 Quantum dots and Ti 3 C 2 After the nano-sheets are compounded, CO and CH 4 Is a pure Cs 2 AgInCl 6 3.15 times of the quantum dot is pure Ti 3 C 2 3.5 times of the nano-sheet. While performing photocatalytic cycle stability test on the same, as shown in FIG. 4 (c), it was found that Cs after three cycles 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst CO 2 The performance of the photocatalytic reduction is not obviously reduced, which indicates that not only CO is obtained after the combination 2 The photocatalytic reduction efficiency is obviously improved, and the photocatalytic stability is also enhanced to a certain extent.
FIG. 5 shows Cs prepared in example 2 of the present invention 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst and Cs prepared in comparative example 3 2 AgBiI 6 And (5) characterizing a result of the morphology microstructure of the quantum dot. FIG. 5 (a) is Cs 2 AgBiI 6 TEM image of Quantum dot, FIG. 5 (b) is Cs 2 AgBiI 6 The HRTEM image of the quantum dot shows that the quantum dot has uniform size, about 10nm in size, good monodispersity and 0.30nm of interplanar spacing, and corresponds to the (022) crystal face. FIG. 5 (c) is Cs 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst TEM image and Cs 2 AgBiI 6 The quantum dots are uniformly dispersed on the surface of the black phosphorus material.
FIG. 6 Cs prepared in example 3 of the present invention 2 AgInBr 6 And (3) a morphological microstructure characterization result of the quantum dot@bismuth alkene composite photocatalyst. FIG. 6 (a) is Cs 2 AgInBr 6 TEM image of the quantum dot@bismuth alkene composite photocatalyst can observe that the quantum dots are uniformly distributed on the surface of the bismuth alkene nano sheet; FIG. 6 (b) is Cs 2 AgInBr 6 HRTEM image of quantum dot@bismuth alkene composite photocatalyst is analyzed through high-angle annular dark field, wherein bismuth alkene nano sheets are square and Cs 2 AgInBr 6 The quantum dots are in six directions.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the claims, which are all within the protection of the present invention.

Claims (8)

1. For CO 2 The composite photocatalyst of the reduced lead-free double perovskite quantum dot@two-dimensional material is characterized in that: the lead-free double perovskite quantum dots and the two-dimensional material are compounded to form a heterojunction structure, and the chemical general formula of the lead-free double perovskite quantum dots is Cs 2 B Ⅰ B Ⅱ X 6 Wherein B is Ⅰ Selected from Ag + ，In + ，Cu + Any one of ions, B Ⅱ Selected from In 3+ ，Bi 3+ ，Sb 3+ X is selected from Cl - ，Br - ，I - Any one ion of the two-dimensional material is selected from Ti 3 C 2 Any one of bismuth alkene and black phosphorus; in particular Cs 2 AgInCl 6 Quantum dot @ Ti 3 C 2 Composite photocatalyst, cs 2 AgBiI 6 Quantum dot @ black phosphorus composite photocatalyst and Cs 2 AgInBr 6 At least one of quantum dot @ bismuth alkene composite photocatalysts; the leadless double perovskite quantum dot@two-dimensional material composite photocatalyst has an I-type heterojunction structure or a II-type heterojunction structure or an S-type heterojunction structure or a Z-type heterojunction structure.
2. A process according to claim 1 for CO 2 The composite photocatalyst of the reduced lead-free double perovskite quantum dot@two-dimensional material is characterized in that: CO of the lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst 2 The reduction product being carbon monoxide CO or methane CH 4 。
3. A method for CO according to any one of claims 1 to 2 2 Reduced leadless double perovskite quantum dot @ two-dimensional materialThe preparation method of the composite photocatalyst is characterized by comprising the following steps:
step 1. Cs is processed 2 CO 3 ， B Ⅰ OAc， B Ⅱ (OAc) 3 Dissolving in octadecene, heating and mixing uniformly under the protection of inert gas;
step 2, dissolving a two-dimensional material in octadecene, dispersing, adding the dispersed material into the product obtained in the step 1, uniformly mixing, adding oleic acid and an oleylamine ligand, and preserving heat until the reaction is complete to obtain a mixed solution;
step 3, heating the mixed solution obtained in the step 2, adding a mixed solution of trimethyl halosilane and hydrochloric acid, and cooling after the reaction is completed;
and 4, centrifuging, washing, drying and grinding the product obtained in the step 3 to obtain the lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst.
4. A method for CO according to claim 3 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst is characterized by comprising the following steps of: in step 1, step 2 and step 3, cs 2 CO 3 、B Ⅰ OAc、B Ⅱ (OAc) 3 The ratio of the two-dimensional material, oleic acid, oleylamine ligand, trimethylhalosilane and hydrochloric acid is 0.1-1mmol:0.2-0.5mmol:0.5-1mmol:30-60mg:1-3mL:1-3mL:1-2mL: 0.3-0.7. 0.7mL.
5. A method for CO according to claim 3 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst is characterized by comprising the following steps of: in step 1, B Ⅰ OAc is AgOAc, B Ⅱ (OAc) 3 For In (OAc) 3 ，Bi(OAc) 3 The inert gas is argon or nitrogen, and the temperature is 100-120 ℃.
6. A method for CO according to claim 3 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst is characterized by comprising the following steps of: in step 2, two dimensionsThe material is Ti 3 C 2 Any one of bismuth alkene and black phosphorus, and the heat preservation temperature is 100-120 ℃.
7. A method for CO according to claim 3 2 The preparation method of the reduced lead-free double perovskite quantum dot@two-dimensional material composite photocatalyst is characterized by comprising the following steps of: in the step 3, the temperature is increased to 170-180 ℃ and the reaction time is 100-180 s; in the step 4, the tertiary butanol solution and the normal hexane solution are adopted for alternate washing, the centrifugation time is 3-7min, the rotating speed is 7000-10000rpm, and the grinding is carried out until no obvious particles exist.
8. A method according to any one of claims 1-2 for CO 2 Reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst or for CO prepared by the preparation method of any one of claims 3-7 2 Reduced lead-free double perovskite quantum dot @ two-dimensional material composite photocatalyst for high-efficiency photocatalytic reduction of CO 2 Is used in the field of applications.
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