CN116786141A - Bromine lead cesium composite photocatalytic material and preparation and application thereof - Google Patents
Bromine lead cesium composite photocatalytic material and preparation and application thereof Download PDFInfo
- Publication number
- CN116786141A CN116786141A CN202310586670.5A CN202310586670A CN116786141A CN 116786141 A CN116786141 A CN 116786141A CN 202310586670 A CN202310586670 A CN 202310586670A CN 116786141 A CN116786141 A CN 116786141A
- Authority
- CN
- China
- Prior art keywords
- cesium
- lead
- bromide
- carbon
- bromine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 96
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 78
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 46
- 239000011022 opal Substances 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 82
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 29
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052794 bromium Inorganic materials 0.000 abstract description 24
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004038 photonic crystal Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract 1
- XQMUOIMHJMRRGK-UHFFFAOYSA-M bromolead Chemical compound [Pb]Br XQMUOIMHJMRRGK-UHFFFAOYSA-M 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a bromine lead cesium composite photocatalytic material, and a preparation method and application thereof. The photocatalysis material is a nano composite material formed by doping carbon points in a lead-bromine cesium inverse opal structure. The organic solution of the lead-cesium bromide enters into the gaps of the photonic crystal template with the polymer microsphere opal structure under the capillary action. And etching the opal template by adopting a carbon dot-toluene solution to obtain a carbon dot-lead bromide cesium inverse opal structure. The reaction condition is mild, the required consumable is cheap, and the operation is simple. The prepared inverse opal structure has the characteristic of three-dimensional order, and the passivation effect of carbon points makes up the surface defect, and is suitable for photocatalytic reduction of CO 2 . When the carbon dot-bromine lead cesium inverse opal structured composite photocatalytic material is applied to photocatalytic carbon dioxide reduction, the CO generation rate of the material reaches 60.25 mu mol g under the irradiation of visible light ‑1 h ‑1 No CH 4 The method has potential application prospect in the field of photocatalytic reduction of carbon dioxide.
Description
Technical Field
The invention belongs to the field of nano composite materials, relates to a bromine lead cesium composite photocatalytic material and preparation and application thereof, and in particular relates to a carbon dot-bromine lead cesium inverse opal structure composite photocatalytic material capable of efficiently and selectively photocatalytic reduction of carbon dioxide and preparation and application thereof.
Background
Conventional fossil energy combustion produces a large amount of carbon dioxide (CO) 2 ) High CO content 2 The greenhouse effect is generated when the water is discharged into the atmosphere, so that the global climate is warmed, glaciers are melted, and the like. In recent years, photocatalytic reduction of CO 2 Techniques, i.e. using light energy to convert CO 2 Is converted into carbon monoxide (CO) and methane (CH) 4 ) The product with equal high added value is considered to be one of effective ways for solving the current energy shortage problem and the greenhouse effect, and has quite research value.
Perovskite materials have achieved remarkable research results in the photoelectric field due to the advantages of adjustable band gap, wide photoresponse range, high photoluminescence quantum yield and the like, and are gradually applied to the photocatalysis field. However, perovskite materials generally have the property of being structurally unstable, wherein all-inorganic perovskite materials lead cesium bromide (CsPbBr) 3 ) Compared with other organic perovskite materials, the organic perovskite material has higher water-meeting and high-temperature environmental stability, and is widely studied. However, due to the disadvantages of few reactive sites and high photo-generated electron-hole recombination, lead cesium bromide alone is used as a photo-catalytic material for photo-catalytic reduction of CO 2 The efficiency is lower, and the selectivity to CO products is lower, which hinders the application of lead-cesium bromide in photocatalytic materials. Therefore, it is important to improve the photocatalytic activity and selectivity of lead cesium bromide by structural design or using other semiconductors as cocatalysts. The inverse opal structure, which is a unique structure of the photonic crystal, has the advantages of larger specific surface area, more exposed active sites, higher light capturing efficiency and the like. Recently, tang Rui prepared Au-CsPbBr 3 Inverse protein structure photocatalyst, and the CO yield is improved to 10.2 mu mol g by means of plasma resonance effect and slow photon effect -1 h -1 (Chemical Engineering Journal,2022,429,132137). However, the photocatalytic efficiency of the lead cesium bromide material with the inverse opal structure is still low, and the material with the inverse opal structure has great development potential in the field of photocatalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bromine lead cesium composite photocatalytic material, and the invention also aims to provide a preparation method of the material, and also aims to provide an application of the bromine lead cesium composite photocatalytic material, which can effectively solve the problems of low photocatalytic activity and insufficient stability of bromine lead cesium and improve the product selectivity of CO.
The technical scheme of the invention is as follows: the bromine lead cesium composite photocatalytic material is characterized by being a composite material formed by doping carbon dots with bromine lead cesium with an inverse opal structure; wherein the mass ratio of the bromine lead cesium to the carbon point is (100-600): 1.
preferably, the lead-cesium bromide of the inverse opal structure has a three-dimensional macroporous structure with a specific surface area of 20-65 m 2 /g。
The invention also provides a method for preparing the lead-cesium bromide composite photocatalytic material, which comprises the following specific steps:
A. preparation of organic solution of lead-cesium bromide
A1. Adding cesium bromide and lead bromide into an organic solution respectively, heating the mixed solution at 50-70 ℃ to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide respectively; wherein, the concentration of cesium bromide in the precursor solution A is 0.2-0.48M, and the concentration of lead bromide in the precursor solution B is 0.24-0.48M;
A2. heating and stirring the precursor solution B, dropwise adding the precursor solution A, continuously reacting for 10-30 min, and cooling to obtain a lead-cesium bromide organic solution, wherein the concentration of the lead-cesium bromide is 0.10-0.24M;
B. preparation of carbon dot-bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking polymer microspheres with opal structures as templates, immersing the lead-bromine-cesium bromide organic solution prepared in the step A into the templates, keeping for 1-5 min, and annealing at 65-85 ℃ to obtain the lead-bromine-cesium bromide opal templates;
B2. adding carbon dots into an alcohol solution for uniform dispersion, wherein the volume ratio of the mass of the carbon dots to the alcohol solution is 5-10 mg/mL; adding the alcohol solution of the carbon dots into toluene and uniformly dispersing again to obtain a carbon dot-toluene mixed solution; wherein, the concentration of the carbon point is 0.05-1 mg/mL;
B3. and C, dripping the carbon dot-toluene mixed solution onto the bromplumbum cesium opal template in the step B1 to remove the polymer microspheres, reacting for 1-10 min, and annealing at 65-85 ℃ to obtain the carbon dot-bromplumbum cesium inverse opal structure composite photocatalytic material.
Preferably, the organic solution in step A1 is dimethyl sulfoxide or N, N-dimethylformamide.
Preferably, in the step A2, the molar ratio of lead to cesium is controlled to be (1.0-1.2) in the process of dropwise adding the precursor solution A into the precursor solution B: 1.
preferably, the polymer microspheres in step B1 are polystyrene or polystyrene grafted acrylic polymers.
Preferably, the alcohol solution in step B2 is absolute ethanol or absolute propanol.
Preferably, the volume ratio of the alcohol solution to toluene in the step B2 is 1: (9-100).
The invention also provides application of the lead-bromine cesium inverse opal structure composite photocatalytic material in photocatalytic reduction of carbon dioxide.
The photocatalysis reaction experiment is that a silicon wafer is placed in a photocatalysis reactor, a certain amount of deionized water is dripped into the inner wall of the reactor, and the reactor is sealed by vacuum grease; ensuring that the inside of the reactor is filled with CO 2 . Photocatalytic reduction of CO using 300W xenon lamp as light source 2 And (5) experiment. The illumination intensity was maintained at a solar level (100 mW/cm 2 ) Constant, continuous irradiation, detection of CO by gas chromatography 2 And (5) reducing the product.
The beneficial effects are that:
1. the invention dopes carbon points on the surface of the inverse opal structure of the lead-bromine cesium without changing CsPbBr 3 Inverse opal structure and its properties. Under illumination, the slow photon effect of the inverse opal structure can effectively slow down the propagation speed of light in the catalyst, improve the light absorption capacity of the catalyst, and promote the separation of photo-generated electron-hole pairs together with the electron transfer and storage capacity of carbon points, so that the composite effect of photo-generated carriersThe rate is reduced, thereby greatly improving the photocatalytic activity of the photocatalytic material. The carbon dot/bromine lead cesium inverse opal structured composite photocatalytic material is applied to photocatalytic reduction of CO 2 Under the irradiation of the sun's visible light (300W xenon lamp), the CO generation rate can reach 60.25 mu mol g at the highest -1 h -1 No CH 4 Production of CO in the photocatalytic reduction of 2 The field has potential application prospect.
2. Compared with semiconductor materials such as noble metal, graphene and the like, the carbon dot and bromine lead cesium perovskite material has the characteristics of simple preparation process, mild preparation conditions and low cost, has good application prospect in the field of photocatalytic reduction, and can provide technical reference for the preparation of other perovskite composite materials.
3. The carbon dot/lead bromide cesium inverse opal structured composite photocatalytic material prepared by the invention reduces CO in photocatalysis 2 No sacrificial agent is added in the process, so that the cost is saved and the pollution to the environment is avoided.
Drawings
FIG. 1 is a flow chart of the preparation of a material according to the present invention;
FIG. 2 is an SEM photograph of the carbon dot/cesium lead bromide inverse opal structure prepared in example 1 of the present invention;
FIG. 3 is a TEM photograph of a carbon dot/lead cesium bromide inverse opal structured composite photocatalytic material prepared in example 1 of the present invention;
FIG. 4 is a high-power transmission electron microscope (HRTEM) photograph of the carbon dot/lead cesium bromide inverse opal structured composite photocatalytic material prepared in example 1 of the present invention;
FIG. 5 is an X-ray electron diffraction (XRD) pattern of the material prepared in example 1 and comparative example 1, wherein curve a is a lead-bromine cesium inverse opal structure, curve b is a carbon dot/lead-bromine cesium inverse opal structure, and curve c is a standard lead-bromine cesium card;
FIG. 6 is a graph showing the comparison of the production rates of photocatalytic carbon dioxide reduction under visible light irradiation of the materials prepared in example 1 and comparative example 1.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to specific examples and comparative examples. It should be understood that the examples are intended to further illustrate the invention and are not intended to limit the scope of the invention.
The flow chart of the preparation of the materials prepared in the following examples is shown in FIG. 1. The preparation of the carbon dots of the following examples is described in reference Highly Photoluminescent Carbon Dots for Multicolor Patterning, sensors, and Bioimaging, professor poplar, university of Jilin.
Example 1
Step 1, preparing a bromine lead cesium organic solution
A1. Adding 0.85g cesium bromide and 1.77g lead bromide into 20mL dimethyl sulfoxide respectively, and heating the mixed solution at 70 ℃ for 30min to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide; wherein, the concentration of cesium bromide is 0.2M, and the concentration of lead bromide is 0.24M;
A2. 10mL of solution B was heated at 70℃with stirring and 12mL of solution A was added dropwise, and the molar ratio of lead to cesium was controlled to 1.2:1, a step of; continuously reacting for 20min, and cooling to room temperature to obtain a dimethyl sulfoxide solution of 0.10M lead-cesium bromide;
step 2, preparation of carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking the opal structure of polystyrene grafted acrylic microspheres as a template, dropwise adding 0.5mL of the dimethyl sulfoxide solution of the lead-bromine cesium prepared in the step 1 to immerse the photonic crystal template, keeping for 5min, and annealing at 65 ℃ to obtain the lead-bromine cesium opal template;
B2. 100mg of a carbon dot rich in carboxyl groups and amino groups (the preparation method of the carbon dot is prepared by hydrothermal reaction of 0.42g of citric acid, 1275. Mu.L of ethylenediamine and 10mL of water at 200 ℃ C. For 5 hours, see the literature Highly Photoluminescent Carbon Dots for Multicolor Patterning, sensors, and Bioimaging of the professor Poplar of Jilin university) was added to 10mL of ethanol solution and kept stirring for 15 minutes, and then 100. Mu.L of the carbon dot ethanol solution was added to 10mL of toluene and kept stirring for 15 minutes to obtain a carbon dot/toluene mixed solution; wherein, the concentration of the carbon point is 0.1mg/mL;
B3. 1mL of carbon dot/toluene mixed solution was added dropwise toRemoving polystyrene grafted acrylic microspheres on the bromplumbum cesium opal template prepared in the step B1, reacting for 2min, and then annealing at 65 ℃ in a vacuum oven to obtain the carbon dot/bromplumbum cesium inverse opal structure composite photocatalytic material, wherein the obtained product is marked as CDs/CsPbBr 3 IOP. Wherein the total mass of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material is 30mg, the mass of the carbon dot is 0.1mg, and the mass ratio of the bromine lead cesium composite material to the carbon dot is 300:1. The specific surface area of the prepared carbon dot/bromine lead cesium inverse opal structure composite material is 65m 2 /g。
FIG. 2 is an SEM photograph of the carbon dot/cesium lead bromide inverse opal structure prepared in this example; it can be seen that the structure of the lead-cesium bromide inverse opal is successfully constructed, and the surface macropores are orderly arranged.
FIG. 3 is a TEM photograph of the carbon dot/lead-cesium bromide inverse opal structured composite photocatalytic material prepared in this example; it can be seen that the carbon sites were successfully doped onto the lead-cesium bromide inverse opal structure.
FIG. 4 is a HRTEM photograph of the carbon dot/lead-bromine cesium inverse opal structured composite photocatalytic material prepared in this example; it can be seen that the interface of the carbon dot and the cesium lead bromide is clearly visible, wherein a lattice spacing of 0.42nm corresponds to the (110) crystal plane of the cesium lead bromide and a lattice spacing of 0.34nm corresponds to the (200) crystal plane of the carbon dot.
Comparative example 1
In order to verify the performance improvement of the carbon dot/bromine plumbum cesium inverse opal structure composite photocatalytic material relative to bromine plumbum cesium inverse opal structure, compared with the embodiment 1, the operation of mixing the carbon dot and toluene solution in the step B2 is omitted, the bromine plumbum cesium inverse opal structure is obtained by directly etching with toluene, and the obtained product is marked as CsPbBr 3 IOP。
Performance test
The materials obtained in example 1 and comparative example 1 were subjected to a photocatalytic reduction carbon dioxide experiment, in which the following steps were performed:
taking 10mg of a sample fixed on a silicon wafer; placing a silicon wafer in a photocatalysis reactor, dripping 1mL of deionized water on the inner wall of the reactor, and sealing the reactor by using vacuum grease; CO is introduced into the reactor 2 For a period of 10min, ensuring that the inside of the reactor is filled with CO 2 . Photocatalytic reduction of CO using 300W xenon lamp as light source 2 And (5) experiment. The illumination intensity was maintained at a solar level (100 mW/cm 2 ) The irradiation was continued for 4 hours and CO was detected by gas chromatography 2 And (5) reducing the product.
The CO yield obtained in example 1 was 241.06. Mu. Mol g for 4 hours -1 Corresponding to a CO yield of 60.25. Mu. Mol.g per hour -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the The CO yield at 4 hours in comparative example 1 was 100.24. Mu. Mol. G -1 Corresponding to a CO yield of 25.06. Mu. Mol.g per hour -1 ·h -1 。
FIG. 5 is an XRD diffraction pattern of the material prepared in example 1 and comparative example 1, wherein curve a is a lead-cesium bromide inverse opal structure, curve b is a carbon dot/lead-cesium bromide inverse opal structure, and curve c is a standard lead-cesium bromide card; it can be seen that diffraction peaks corresponding to cubic lead cesium bromide in the carbon dot/lead cesium bromide inverse opal structured composite occur.
FIG. 6 is a graph showing the comparison of the rate of formation of the photocatalytic carbon dioxide reduction products under visible light irradiation for the materials prepared in example 1 and comparative example 1; as can be seen, CDs/CsPbBr 3 The CO formation rate of IOP reaches 60.25 mu mol g -1 h -1 Far exceeding CsPbBr 3 The reduction efficiency of the IOP shows the ultrahigh photocatalytic activity of the material prepared by the invention.
Example 2
Step 1, preparing a bromine lead cesium organic solution
A1. Adding 1.02g of cesium bromide and 1.77g of lead bromide into 20mLN, N-dimethylformamide respectively, and heating the mixed solution at 70 ℃ for 30min to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide; wherein, the concentration of cesium bromide is 0.24M, and the concentration of lead bromide is 0.24M;
A2. 10mL of solution B was heated at 70℃with stirring and 10mL of solution A was added dropwise, and the molar ratio of lead to cesium was controlled to be 1:1, a step of; continuously reacting for 20min, and cooling to room temperature to obtain an N, N-dimethylformamide solution of 0.12M lead-cesium bromide;
step 2, preparation of carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking the opal structure of polystyrene microspheres as a template, dropwise adding 0.5mL of the N, N-dimethylformamide solution of the lead-bromine cesium prepared in the step 1 to submerge the photonic crystal template, keeping for 5min, and annealing at 85 ℃ to obtain the lead-bromine cesium opal template;
B2. 100mg of carbon dots (the preparation method of the carbon dots is the same as that of example 1) is added into 10mL of ethanol solution and kept stirring for 15min, and then 100 mu L of the carbon dot ethanol solution is added into 10mL of toluene and kept stirring for 15min, so as to obtain a carbon dot/toluene mixed solution; wherein, the concentration of the carbon point is 0.1mg/mL;
B3. and D, dripping 1mL of carbon dot/toluene mixed solution onto the bromplumbum cesium opal template prepared in the step B1 to remove polystyrene microspheres, reacting for 2min, and annealing at 85 ℃ in a vacuum oven to obtain the carbon dot/bromplumbum cesium inverse opal structure composite photocatalytic material. Wherein the total mass of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material is 30mg, the mass of the carbon dot is 0.1mg, and the mass ratio of the bromine lead cesium composite material to the carbon dot is 300:1. The specific surface area of the prepared carbon dot/bromine lead cesium inverse opal structure composite material is 50m 2 /g。
The composite material of the carbon dot-bromine lead cesium inverse opal structure prepared in the embodiment successfully constructs the bromine lead cesium inverse opal structure, and the surface macropores are orderly arranged; and the carbon points are successfully doped on the lead-bromine cesium inverse opal structure.
Experiments on photocatalytic reduction of carbon dioxide As in example 1, a CO yield of 205.20. Mu. Mol. G was obtained for 4 hours in example 2 -1 Corresponding to a CO yield of 51.3. Mu. Mol. G per hour -1 ·h -1 ；
Example 3
Step 1, preparing a bromine lead cesium organic solution
A1. Adding 2.04g of cesium bromide and 3.54g of lead bromide into 20mL of dimethyl sulfoxide respectively, and heating the mixed solution at 70 ℃ for 30min to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide; wherein, the concentration of cesium bromide is 0.48M, and the concentration of lead bromide is 0.48M;
A2. 10mL of solution B was heated at 50deg.C with stirring and 10mL of solution A was added dropwise, and the molar ratio of lead to cesium was controlled to be 1:1, a step of; continuously reacting for 20min, and cooling to room temperature to obtain a dimethyl sulfoxide solution of 0.24M lead-cesium bromide;
step 2, preparation of carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking the opal structure of the polystyrene grafted acrylic microspheres as a template, dropwise adding 1.5mL of the DMSO solution of the lead-bromine cesium prepared in the step 1 to submerge the photonic crystal template, keeping for 5min, and annealing at 65 ℃ to obtain the lead-bromine cesium opal template;
B2. 100mg of carbon dots (the preparation method of the carbon dots is the same as that of example 1) is added into 10mL of ethanol solution and kept stirring for 15min, and then 1mL of carbon dot ethanol solution is added into 9mL of toluene and kept stirring for 15min, so as to obtain a carbon dot/toluene mixed solution; wherein the concentration of the carbon dots is 1mg/mL;
B3. dropwise adding 1mL of carbon dot/toluene mixed solution onto the bromplumbum cesium opal template prepared in the step B1 to remove polystyrene microspheres, reacting for 10min, and then annealing at 65 ℃ in a vacuum oven to obtain the carbon dot/bromplumbum cesium inverse opal structure composite photocatalytic material, wherein the obtained product is marked as CDs/CsPbBr 3 IOP. Wherein the total mass of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material is 100mg, the mass of the carbon dot is 1mg, and the mass ratio of the bromine lead cesium composite material to the carbon dot is 100:1. The specific surface area of the prepared carbon dot/bromine lead cesium inverse opal structure composite material is 20m 2 /g。
The composite material of the carbon dot-bromine lead cesium inverse opal structure prepared in the embodiment successfully constructs the bromine lead cesium inverse opal structure, and the surface macropores are orderly arranged; and the carbon points are successfully doped on the lead-bromine cesium inverse opal structure.
Experiments on carbon dioxide by photocatalytic reduction were carried out in the same manner as in example 1 to obtain a CO yield of 175.20. Mu. Mol. G for 4 hours in example 3 -1 Corresponding to a CO yield of 43.8. Mu. Mol.g per hour -1 ·h -1 ；
Example 4
The preparation method of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material comprises the following steps:
step 1, preparing a bromine lead cesium organic solution
A1. Adding 1.70g cesium bromide and 3.54g lead bromide into 20mL dimethyl sulfoxide respectively, and heating the mixed solution at 70 ℃ for 30min to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide; wherein, the concentration of cesium bromide is 0.4M, and the concentration of lead bromide is 0.48M;
A2. 10mL of solution B was heated at 50deg.C with stirring and 10mL of solution A was added dropwise, and the molar ratio of lead to cesium was controlled to be 1.2:1, a step of; continuously reacting for 20min, and cooling to room temperature to obtain a dimethyl sulfoxide solution of 0.2M lead-cesium bromide;
step 2, preparation of carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking the opal structure of the polystyrene grafted acrylic microspheres as a template, dropwise adding 0.5mL of the DMSO solution of the lead-bromine cesium prepared in the step 1 to submerge the photonic crystal template, keeping for 5min, and annealing at 65 ℃ to obtain the lead-bromine cesium opal template;
B2. 50mg of carbon dots (the preparation method of the carbon dots is the same as that of example 1) is added into 10mL of propanol solution and kept stirring for 15min, and then 100 mu L of carbon dot propanol solution is added into 10mL of toluene and kept stirring for 15min, so as to obtain a carbon dot/toluene mixed solution; wherein the final mass concentration of the carbon dots is 0.05mg/mL;
B3. dropwise adding 1mL of carbon dot/toluene mixed solution onto the bromplumbum cesium opal template prepared in the step B1 to remove polystyrene microspheres, reacting for 10min, and then annealing at 65 ℃ in a vacuum oven to obtain the carbon dot/bromplumbum cesium inverse opal structure composite photocatalytic material, wherein the obtained product is marked as CDs/CsPbBr 3 IOP. Wherein the total mass of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material is 30mg, the mass of the carbon dot is 0.05mg, and the mass ratio of the bromine lead cesium composite material to the carbon dot is 600:1. The specific surface area of the prepared carbon dot/bromine lead cesium inverse opal structure composite material is 30m 2 /g。
The composite material of the carbon dot-bromine lead cesium inverse opal structure prepared in the embodiment successfully constructs the bromine lead cesium inverse opal structure, and the surface macropores are orderly arranged; and the carbon points are successfully doped on the lead-bromine cesium inverse opal structure.
Experiments on photocatalytic reduction of carbon dioxide As in example 1, a CO yield of 186.45. Mu. Mol. G was obtained in example 4 for 4 hours -1 Corresponding to a CO yield of 46.61. Mu. Mol. G per hour -1 ·h -1 ；
Example 5
The preparation method of the carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material comprises the following steps:
step 1, preparing a bromine lead cesium organic solution
A1. Adding 0.85g cesium bromide and 1.77g lead bromide into 20mL dimethyl sulfoxide respectively, and heating the mixed solution at 50 ℃ for 30min to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide; wherein, the concentration of cesium bromide is 0.2M, and the concentration of lead bromide is 0.24M;
A2. 10mL of solution B was heated at 70℃with stirring and 10mL of solution A was added dropwise, and the molar ratio of lead to cesium was controlled to 1.2:1, a step of; continuously reacting for 20min, and cooling to room temperature to obtain a dimethyl sulfoxide solution of 0.10M lead-cesium bromide;
step 2, preparation of carbon dot/bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking the opal structure of the polymer microsphere as a template, dropwise adding 0.5mL of the dimethyl sulfoxide solution of the lead-bromine cesium prepared in the step 1 to immerse the photonic crystal template, keeping for 1min, and annealing at 65 ℃ to obtain the lead-bromine cesium opal template;
B2. 100mg of carbon dots (the preparation method of the carbon dots is the same as that of example 1) is added into 10mL of propanol solution and kept stirring for 15min, and then 100 mu L of carbon dot propanol solution is added into 10mL of toluene and kept stirring for 15min, so as to obtain a carbon dot/toluene mixed solution; wherein the final mass concentration of the carbon dots is 0.1mg/mL;
B3. dropwise adding 1mL of carbon dot/toluene mixed solution to the bromplumbum cesium opal template prepared in the step B1 to remove polystyrene grafted acrylic microspheres, reacting for 1min, and then annealing at 65 ℃ in a vacuum oven to obtain the carbon dot/bromplumbum cesium inverse opal structure composite photocatalytic material, wherein the obtained product is marked as CDs/CsPbBr 3 IOP. Wherein carbon dot/bromine lead cesium inverse opal structure composite photocatalysis materialThe total mass of the (C) is 30mg, the mass of the carbon point is 0.1mg, and the mass ratio of the bromine lead cesium composite material to the carbon point is 300:1. The specific surface area of the prepared carbon dot/bromine lead cesium inverse opal structure composite material is 45m 2 /g。
The composite material of the carbon dot-bromine lead cesium inverse opal structure prepared in the embodiment successfully constructs the bromine lead cesium inverse opal structure, and the surface macropores are orderly arranged; and the carbon points are successfully doped on the lead-bromine cesium inverse opal structure.
Experiments on carbon dioxide by photocatalytic reduction were carried out in the same manner as in example 1 to obtain a CO yield of 124.64. Mu. Mol. G for 4 hours in example 5 -1 Corresponding to a CO yield of 31.16. Mu. Mol.g per hour -1 ·h -1 ；
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; while the invention has been described with reference to the foregoing embodiments, it should be understood that: it is still possible to modify the steps described in the foregoing embodiments; such modifications and substitutions do not depart from the essence of the corresponding steps from the scope of the embodiments of the present invention.
Claims (9)
1. The bromine lead cesium composite photocatalytic material is characterized by being a composite material formed by doping carbon dots with bromine lead cesium with an inverse opal structure; wherein the mass ratio of the bromine lead cesium to the carbon point is (100-600): 1.
2. the composite photocatalytic material with the inverse opal structure of lead bromide and cesium according to claim 1, which is characterized in that the lead bromide and cesium with the inverse opal structure has a three-dimensional macroporous structure and a specific surface area of 20-65 m 2 /g。
3. A method for preparing the lead-cesium bromide composite photocatalytic material according to claim 1, which comprises the following specific steps:
A. preparation of organic solution of lead-cesium bromide
A1. Adding cesium bromide and lead bromide into an organic solution respectively, heating the mixed solution at 50-70 ℃ to obtain a precursor solution A of cesium bromide and a precursor solution B of lead bromide respectively; wherein, the concentration of cesium bromide in the precursor solution A is 0.2-0.48M, and the concentration of lead bromide in the precursor solution B is 0.24-0.48M;
A2. heating and stirring the precursor solution B, dropwise adding the precursor solution A, continuously reacting for 10-30 min, and cooling to obtain a lead-cesium bromide organic solution, wherein the concentration of the lead-cesium bromide is 0.10-0.24M;
B. preparation of carbon dot-bromine lead cesium inverse opal structure composite photocatalytic material
B1. Taking polymer microspheres with opal structures as templates, immersing the lead-bromine-cesium bromide organic solution prepared in the step A into the templates, keeping for 1-5 min, and annealing at 65-85 ℃ to obtain the lead-bromine-cesium bromide opal templates;
B2. adding carbon dots into an alcohol solution for uniform dispersion, wherein the volume ratio of the mass of the carbon dots to the alcohol solution is 5-10 mg/mL; adding the alcohol solution of the carbon dots into toluene and uniformly dispersing again to obtain a carbon dot-toluene mixed solution; wherein, the concentration of the carbon point is 0.05-1 mg/mL;
B3. and C, dripping the carbon dot-toluene mixed solution onto the bromplumbum cesium opal template in the step B1, reacting for 1-10 min, and annealing at 65-85 ℃ to obtain the carbon dot-bromplumbum cesium inverse opal structure composite photocatalytic material.
4. A process according to claim 3, characterized in that the organic solution in step A1 is dimethyl sulfoxide or N, N-dimethylformamide.
5. A method according to claim 3, characterized in that the molar ratio of lead to cesium is controlled to be (1.0-1.2) during the dropwise addition of the precursor solution B in step A2: 1.
6. a method according to claim 3, characterized in that the polymer microspheres in step B1 are polystyrene or polystyrene grafted acrylic polymers.
7. A process according to claim 3, wherein the alcoholic solution in step B2 is absolute ethanol or absolute propanol.
8. A process according to claim 3, characterized in that the volume ratio of the alcoholic solution to toluene in step B2 is 1: (9-100).
9. Use of the lead-bromide cesium inverse opal structured composite photocatalytic material according to claim 1 in photocatalytic reduction of carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310586670.5A CN116786141A (en) | 2023-05-24 | 2023-05-24 | Bromine lead cesium composite photocatalytic material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310586670.5A CN116786141A (en) | 2023-05-24 | 2023-05-24 | Bromine lead cesium composite photocatalytic material and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116786141A true CN116786141A (en) | 2023-09-22 |
Family
ID=88033854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310586670.5A Pending CN116786141A (en) | 2023-05-24 | 2023-05-24 | Bromine lead cesium composite photocatalytic material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116786141A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113244935A (en) * | 2021-05-17 | 2021-08-13 | 电子科技大学长三角研究院(湖州) | In-situ generated perovskite heterojunction photocatalyst and preparation method thereof |
| CN114557478A (en) * | 2022-01-12 | 2022-05-31 | 华南师范大学 | Photocatalytic degradation filter cigarette holder and preparation method thereof |
| CN114950500A (en) * | 2022-02-24 | 2022-08-30 | 电子科技大学长三角研究院(湖州) | Preparation method and application of bismuth/cesium lead bromide composite photocatalytic material |
| KR20220154543A (en) * | 2021-05-13 | 2022-11-22 | 경북대학교 산학협력단 | Zeolitic Quantum Dots and Preparing Method Thereof |
-
2023
- 2023-05-24 CN CN202310586670.5A patent/CN116786141A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220154543A (en) * | 2021-05-13 | 2022-11-22 | 경북대학교 산학협력단 | Zeolitic Quantum Dots and Preparing Method Thereof |
| CN113244935A (en) * | 2021-05-17 | 2021-08-13 | 电子科技大学长三角研究院(湖州) | In-situ generated perovskite heterojunction photocatalyst and preparation method thereof |
| CN114557478A (en) * | 2022-01-12 | 2022-05-31 | 华南师范大学 | Photocatalytic degradation filter cigarette holder and preparation method thereof |
| CN114950500A (en) * | 2022-02-24 | 2022-08-30 | 电子科技大学长三角研究院(湖州) | Preparation method and application of bismuth/cesium lead bromide composite photocatalytic material |
Non-Patent Citations (1)
| Title |
|---|
| ZHOU ET AL.: "Slow-Photon-Effect-Induced Photoelectrical-Conversion Efficiency Enhancement for Carbon-Quantum-Dot-Sensitized Inorganic CsPbBr3 Inverse Opal Perovskite Solar Cells", 《ADVANCED MATERIALS》, vol. 29, no. 43, 10 October 2017 (2017-10-10), pages 1 - 9 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Ultra-thin tubular graphitic carbon Nitride-Carbon Dot lateral heterostructures: One-Step synthesis and highly efficient catalytic hydrogen generation | |
| Song et al. | Enhanced light utilization efficiency and fast charge transfer for excellent CO2 photoreduction activity by constructing defect structures in carbon nitride | |
| CN106964339B (en) | Carbon-doped ultrathin bismuth tungstate nanosheet photocatalytic material and preparation method thereof | |
| CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
| CN108479833B (en) | Preparation method and application of oxygen-doped carbon nitride aerogel photocatalyst | |
| CN106390986B (en) | A kind of preparation method of pucherite/strontium titanates composite photo-catalyst | |
| CN108993574B (en) | Preparation method of high-performance graphite-phase carbon nitride photocatalytic material | |
| CN112076777B (en) | For CO2Reduced photocatalyst and preparation method thereof | |
| CN112517043B (en) | Nitrogen vacancy and hydroxyl synergistically modified graphite-phase carbon nitride photocatalyst, preparation method thereof and application thereof in photocatalytic hydrogen production | |
| CN113198496B (en) | Metallic indium-doped lead cesium bromide perovskite quantum dot photocatalyst, preparation method and application thereof in reduction of carbon dioxide | |
| CN111215118A (en) | Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof | |
| CN112439416A (en) | Preparation method and application of high-dispersion copper-loaded titanium dioxide nanosheet | |
| Yu et al. | Controllable growth of coral-like CuInS2 on one-dimensional SiO2 nanotube with super-hydrophilicity for enhanced photocatalytic hydrogen evolution | |
| CN114950500A (en) | Preparation method and application of bismuth/cesium lead bromide composite photocatalytic material | |
| CN109701577B (en) | Method for preparing porous graphite phase carbon nitride by using carbon nano tube as hard template | |
| CN113769764B (en) | CdS/Cu 7 S 4 /CdMoO 4 Preparation method and application of nano heterostructure | |
| CN108940343B (en) | Fe-TiO2nanotube/g-C3N4Composite material and preparation method and application thereof | |
| CN108855193B (en) | TaN/BiVO4Heterojunction composite material and preparation method and application thereof | |
| CN116786141A (en) | Bromine lead cesium composite photocatalytic material and preparation and application thereof | |
| CN108607589B (en) | TiN-In2S3Preparation method and application of nano composite photocatalyst | |
| CN110841688A (en) | Preparation method of co-catalyst based on self-assembled carbon nitride sphere/sheet homomorphic junctions | |
| Li et al. | Ordered porous nitrogen-vacancy carbon nitride for efficient visible-light hydrogen evolution | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof | |
| CN114452998A (en) | Preparation method and application of multi-walled carbon nanotube and graphitized carbon nitride composite material | |
| CN112871165A (en) | Two-dimensional WO modified by noble metal loading3Preparation method of nanosheet photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |