CN113856755B - CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material and preparation method and application thereof - Google Patents
CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- CN113856755B CN113856755B CN202111162811.8A CN202111162811A CN113856755B CN 113856755 B CN113856755 B CN 113856755B CN 202111162811 A CN202111162811 A CN 202111162811A CN 113856755 B CN113856755 B CN 113856755B
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 101
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- 238000002360 preparation method Methods 0.000 title claims description 24
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
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- 239000011941 photocatalyst Substances 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 7
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- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
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- 239000013473 2D covalent-organic framework Substances 0.000 description 1
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 150000007857 hydrazones Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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Abstract
CsPbBr 3‑x I x Quantum dot@COF-5 composite photocatalytic material and CsPbBr 3‑x I x The quantum dots grow on the surface of the COF-5 material in situ, and CsPbBr at the same time 3‑x I x The quantum dots are connected with the COF-5 material through chemical bond cesium boron oxygen bonds (Cs-B-O) and are arranged on CsPbBr 3‑ x I x In the quantum dot, the range of x is more than or equal to 0 and less than or equal to 3, the quantum dot has the advantages of good crystallinity, rich active sites and the like, and the COF-5 material and CsPbBr are combined 3‑x I x Quantum dot compounding, forming I-type or II-type (Z-type or S-type) heterojunction structure according to difference of band gap matching structures and different transmission directions of photo-generated electrons, and realizing CsPbBr 3‑x I x The quantum dots grow on the surface of the COF-5 material in situ, the carrier rate is improved, the recombination of photo-generated electron-hole pairs is reduced through chemical bond connection, the chemical bond effect is not only beneficial to the transmission of photoelectric carriers, but also enhances the photocatalysis CO 2 Reduction efficiency is improved to CO 2 Photocatalytic reduction performance and CsPbBr improvement 3‑x I x Stability of the quantum dot @ COF-5 composite photocatalytic material.
Description
Technical Field
The invention relates to the technical field of composite photocatalysts and preparation methods thereof, in particular to a method for preparing the sameIt relates to a CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material and preparation method and application thereof.
Background
Since the industrial revolution, the overuse of fossil fuels in the world has caused energy shortages and serious environmental problems. Photocatalysis, which is a "green" sustainable technology for converting solar energy into chemical energy, is considered as a promising strategy for alleviating environmental problems such as greenhouse effect. The semiconductor photocatalyst plays a vital role in the photocatalysis, in the photocatalysis process, the semiconductor absorbs photons with energy higher than the band gap of the semiconductor, thereby generating photo-generated electrons and holes which are respectively migrated to a Conduction Band (CB) and a Valence Band (VB) of the semiconductor, the photo-generated electrons and the holes perform oxidation reduction reaction with an electron acceptor and a donor, and the photo-generated electrons have extremely strong reducibility with CO 2 The action generates CO and CH 4 HCHO, etc. At present, most of the photo-catalytic photo-response range is concentrated in the ultraviolet light region, and the utilization rate of visible light still needs to be improved, so that the practical application of the photo-catalysis is still a challenge, and finding a high-efficiency, stable and visible light-responsive photo-catalyst is still the core of the photo-catalysis field.
In recent years, researchers have been devoted to the study of polymer semiconductors as photocatalysts, such as graphitic carbon nitride (g-C 3 N 4 ) Conjugated polymers and Covalent Organic Frameworks (COFs). COFs have periodic organic units, high thermal and chemical stability, high porosity, large surface area, pi conjugated structures and pi-pi stacked layers, as well as broad visible light absorption ranges and high charge separation efficiency. COFs have high crystallinity and high porosity, and are formed by covalent bonding integration of specific connecting groups such as imine bonds, boroxine, borate, hydrazone, azine or ketoenamine through organic polymers formed by periodic arrangement of different chemical bonds. The connection units with different structures and sizes are constructed, so that the two-dimensional (2D) or three-dimensional (3D) COF can be prepared, and the pore size of the connection units is adjustable. The polygonal channel structure and the pore wall enable the surface of the polygonal channel structure and the pore wall to have rich active sites, and the polygonal channel structure and the pore wall can be used as catalytic reaction active sites to promote the excitons to be capable of migrating rapidly. COFs have the following advantages as photocatalysts:
1) The structure is adjustable: the topology, channel and band structure of COFs are tuned by introducing different molecular building blocks.
2) Rich active sites: the nanoscale pore structure leads to the higher specific surface area, and the surface has rich active sites, thereby being beneficial to the adsorption of reactants and the progress of photocatalytic reaction.
3) Structural stability: the structural units of the COFs are connected through covalent bonds, so that the COFs have very high excellent thermal stability and chemical stability, and the stability of the photocatalyst is improved.
4) COFs used as photocatalysts consist of electron donor-acceptor (D-a), and the migration of photogenerated electrons from the donor to the acceptor is advantageous in improving the efficiency of separation of photoelectron-hole pairs.
5) The periodic ordered columnar array of the pi conjugated system is beneficial to electron delocalization, so that the COFs have excellent electron transmission performance and outstanding photoelectric properties.
Disclosure of Invention
It is an object of the present invention to provide a CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material, and chemical bond Cs-B-O serving as photogenerated carrier transmission channel is beneficial to reducing photogenerated electron-hole recombination, so that CO is improved 2 Photocatalytic reduction reaction efficiency.
It is a second object of the present invention to provide CsPbBr 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material is simple in process, good in reproducibility and high in selectivity.
It is a further object of the present invention to provide a CsPbBr 3-x I x Application of quantum dot@COF-5 composite photocatalytic material.
One of the technical schemes adopted for realizing the purpose of the invention is as follows:
CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material and CsPbBr 3-x I x The quantum dots grow on the surface of the COF-5 material in situ, and CsPbBr at the same time 3-x I x The quantum dots are connected with the COF-5 material through chemical bond cesium boron oxygen bonds (Cs-B-O)At CsPbBr 3-x I x In the quantum dot, x is more than or equal to 0 and less than or equal to 3.
In the technical scheme, the halogen precursor PbBr is controlled 2 :PbI 2 Preparing different quantum dots, pbBr in proportion 2 :PbI 2 The ratio was varied from 0:3 to 3:0, respectively obtaining different CsPbBr 3-x I x Quantum dots. CsPbBr 3-x I x The quantum dots can be CsPbBr 3 Quantum dot or CsPbI 3 Quantum dot or CsPbBri 2 Quantum dot or CsPbBr 2 I quantum dots or CsPbBr 1.5 I 1.5 Quantum dots.
In the technical scheme, the CsPbBr 3-x I x CsPbBr in quantum dot @ COF-5 composite photocatalytic material 3-x I x The mass percentage of the quantum dots is 20% -60%.
In the technical scheme, the CsPbBr 3-x I x The quantum dot@COF-5 composite photocatalytic material forms an I-type heterojunction structure or an II-type heterojunction structure or an S-type heterojunction structure or a Z-type heterojunction structure according to the difference of band gap matching structures and different photogenerated electron transmission directions.
In the technical proposal, the boric acid ester group in the COF-5 material and CsPbBr 3-x I x Cesium ions (Cs) of quantum dots + ) Condensation reaction occurs to form cesium boron oxide (Cs-B-O) bonds.
In the technical scheme, the COF-5 material is in a two-dimensional sheet structure.
The second technical scheme for realizing the purpose of the invention is as follows:
CsPbBr 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material is characterized by comprising the following steps of:
A1. taking the COF-5 material, washing, drying and grinding after heat treatment to obtain COF-5 material powder;
A2. respectively weighing the COF-5 material powder obtained in the step A1 and a reaction precursor, mixing, dissolving in octadecene, uniformly mixing and heating in an inert gas atmosphere, adding oleic acid and oleic acid ligand, and preserving the temperature until the reaction is complete;
A3. continuously heating the product obtained in the step 2, then adding cesium acetate solution, reacting, and cooling to obtain a mixed solution;
A4. centrifuging, washing, drying and grinding the mixed solution obtained in the step 3 to obtain CsPbBr 3-x I x Quantum dot @ COF-5 composite photocatalytic material.
In the technical scheme, in the step A2 and the step A3, the proportion of the COF-5 material powder, the Pb-containing precursor, the octadecene, the oleic acid ligand and the cesium acetate is 200-400mg:1-2mmol:10-30mL:1-3mL:1-3mL:0.3-0.6mmol.
In the above technical scheme, in step A2, the reaction precursor is PbBr 2 Or PbI 2 Or PbBr 2 And PbI 2 Wherein PbBr is selected from the group consisting of 2 ：PbI 2 The ratio of (3) to (n): n, n is in the range of 0.ltoreq.n.ltoreq.3, preferably n is 0 or 1 or 1.5 or 2.
In the technical scheme, in the step A1, the heat treatment temperature is 100-120 ℃ to remove water possibly existing in the solution, acetone and dimethyl diamide are adopted for washing for many times, in the step A2, the heating temperature and the heat preservation temperature are 100-120 ℃, in the step A3, the heating is continued until the temperature is 160-180 ℃, in the step A4, the tertiary butanol solution and the normal hexane solution are adopted for washing alternately, the centrifugal time is 3-10min, the rotating speed is 8000-10000rpm, the drying temperature is 60-80 ℃, and the grinding is carried out until no obvious particles exist.
In the technical scheme, the preparation method of the COF-5 material in the step A1 comprises the following steps:
step B1, adding 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-benzene diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the addition ratio of 0.4-0.8 mmol to 0.6-1.4 mmol to 10-15 mL in an anhydrous and anaerobic environment, and adding 2,3,6,7,10, 11-hexahydroxy triphenyl and 1, 4-benzene diboronic acid into the mixed solution of 1,3, 5-trimethylbenzene and 1, 4-dioxane to form a mixture;
b2, sealing the mixture, performing ultrasonic dispersion, and oscillating to obtain uniform dispersion liquid;
b3, heating the dispersion liquid to a certain temperature, and reacting for a period of time;
and B4., washing a reaction product, then carrying out vacuum drying, finally introducing protective gas, and carrying out heat treatment on the product for a period of time at a set temperature to obtain the two-dimensional flaky COF-5 material.
The scheme adopted for achieving the third purpose of the invention is as follows:
according to the CsPbBr 3-x I x Quantum dot @ COF-5 composite photocatalytic material or CsPbBr prepared by using preparation method 3-x I x Quantum dot@COF-5 composite photocatalytic material for efficiently reducing CO by photocatalysis 2 Or hydrolysis hydrogen production or organic pollutant degradation.
CsPbBr prepared by in situ growth 3-x I x Quantum dot@COF-5 photocatalytic material with COF-5 as substrate material and CsPbBr 3-x I x The quantum dots provide growth sites such that CsPbBr 3-x I x The quantum dots are stably dispersed on the surface of the COF-5 material, and CsPbBr with different band gap structures 3-x I x The quantum dots are matched with the COF-5 to form a type I or type II (Z type and S type) heterojunction structure, so that the recombination efficiency of photo-generated electron-hole pairs is reduced, and the light response range is prolonged; at the same time CsPbBr 3-x I x Cesium boron oxide (Cs-B-O) bonds are formed between the quantum dots and the COF-5 material, and the connection of chemical bonds can be used as a carrier migration channel, so that the recombination of photo-generated electrons and holes is reduced, and the CO is improved 2 Photocatalytic reduction efficiency. The Pb-containing precursor is used as halogen source, and specifically PbBr can be used 2 Or PbI 2 Or PbBr 2 And PbI 2 Is used for preparing CsPbBr 3-x I x Quantum dots. With the increase of the content of the I element, the light absorption boundary of the quantum dot is subjected to red shift, the forbidden bandwidth is reduced, and CO is affected 2 Photocatalytic reduction product selectivity.
The beneficial effects of the invention are as follows:
1.CsPbBr 3-x I x the quantum dot@COF-5 composite photocatalytic material has the advantages of good crystallinity, abundant active sites and the like, and the COF-5 material and CsPbBr are combined 3-x I x Quantum dot recombination, according to the difference of band gap matching structures, the transmission directions of the photo-generated electrons are different, and an I-type or II-type (Z-type and S-type) heterojunction structure is formed, thereby realizing CsPbBr 3-x I x The quantum dots grow on the surface of the COF-5 material in situ, the carrier rate is improved, the recombination of photo-generated electron-hole pairs is reduced through chemical bond connection, the chemical bond effect is not only beneficial to the transmission of photoelectric carriers, but also enhances the photocatalysis CO 2 Reduction efficiency is improved to CO 2 Photocatalytic reduction performance and CsPbBr improvement 3-x I x Stability of the quantum dot @ COF-5 composite photocatalytic material.
2.CsPbBr 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material has the advantages of simple process, good reproducibility, high selectivity, simple process, good reproducibility, low raw material cost and environment friendliness.
3.CsPbBr 3-x I x Quantum dot @ COF-5 composite photocatalytic material can be used for photocatalytic reduction of CO 2 Or in the practical application of hydrogen production by hydrolysis or degradation of organic pollutants.
Drawings
FIG. 1 shows the COF-5 material prepared in comparative example 1 and CsPbBr prepared in comparative example 2 3 Quantum dots and CsPbBr prepared in example 1 3 XRD pattern of quantum dot@COF-5 composite photocatalytic material.
FIG. 2 is CsPbBr obtained in comparative example 2 3 Quantum dot, csPbBr prepared in comparative example 3 1.5 I 1.5 Quantum dot, csPbI prepared in comparative example 4 3 And (5) characterizing the morphology of the quantum dots. Wherein FIG. 2 (a) is CsPbBr 3 HRTEM image of Quantum dots, FIG. 2 (b) CsPbBr 1.5 I 1.5 HRTEM image of Quantum dots, FIG. 2 (c) CsPbI 3 HRTEM images of quantum dots.
FIG. 3 shows the COF-5 material prepared in comparative example 1 and CsPbBr prepared in comparative example 2 3 Quantum dots and CsPbBr prepared in example 1 3 UV-Vis spectrum of quantum dot @ COF-5 composite photocatalytic material.
FIG. 4 shows the COF-5 material prepared in comparative example 1 and CsPbI material prepared in comparative example 4 3 Quantum dots and CsPbI prepared in example 3 3 IR spectrum diagram of quantum dot @ COF-5 composite photocatalytic material.
FIG. 5 preparation of COF-5 material prepared in comparative example 1, comparative example 2CsPbBr of (A) 3 Quantum dots and CsPbBr prepared in example 1 3 The photocatalytic reduction efficiency curve of the quantum dot @ COF-5 composite photocatalytic material is shown in FIG. 5 (a) as a CO yield curve under UV-Vis illumination and FIG. 5 (b) as a CH under UV-Vis illumination 4 Yield curve, fig. 5 (c) is a CO yield curve under Vis illumination.
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 COF-5 material used in the following examples was disclosed in patent publication No. CN 111057246A: the COF-5 two-dimensional flaky crystal material is prepared by a preparation method recorded in a preparation method of the COF-5 two-dimensional flaky crystal material.
Example 1
CsPbBr provided in example 1 3 The preparation method of the quantum dot@COF-5 composite photocatalytic material comprises the following steps:
A1. taking a COF-5 material, performing heat treatment at 120 ℃ for 72 hours, adopting acetone and dimethyl diamide to wash for many times, and grinding after vacuum drying to obtain COF-5 material powder;
A2. 200mg of the COF-5 material powder obtained in the step A1 and 1mmol of PbBr were weighed respectively 2 Mixing, dissolving in 20mL of Octadecene (ODE), uniformly mixing and stirring under argon atmosphere, heating to 100 ℃, adding 1mL of Oleic Acid (OA) and 1mL of oleic acid ligand (OLA), and preserving heat for 1h until complete dissolution;
A3. continuously heating the product obtained in the step 2 to 160 ℃, then rapidly injecting 1mL of 0.3mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
A4. centrifugally washing the mixed solution obtained in the step 3 by using a tertiary butanol solution, centrifuging at 10000rpm for 7min, and taking precipitate; then the normal hexane solution is utilized to rotate at 8000rpm, the mixture is centrifuged for 4min to obtain sediment, and the steps are repeated for 2 times to obtain the sedimentDrying at 60deg.C for 12 hr, grinding for 5min until no obvious granule exists, to obtain CsPbBr 3 Quantum dot @ COF-5 composite photocatalytic material.
Example 2
Example 2 CsPbBr 1.5 I 1.5 The preparation method of the quantum dot@COF-5 composite photocatalytic material comprises the following steps:
A1. taking a COF-5 material, performing heat treatment at 120 ℃ for 72 hours, adopting acetone and dimethyl diamide to wash for many times, and grinding after vacuum drying to obtain COF-5 material powder;
A2. 300mg of the COF-5 material powder obtained in the step A1 and 1.5mmol of PbBr were weighed separately 2 、1.5mmol PbI 2 After mixing, dissolving in 30mL of Octadecene (ODE), uniformly mixing and stirring under argon atmosphere, heating to 120 ℃, then adding 2.5mL of Oleic Acid (OA) and 2.5mL of Oleylamine Ligand (OLA), and preserving heat for 1h until complete dissolution;
A3. continuously heating the product obtained in the step 2 to 170 ℃, then rapidly injecting 1mL of 0.6mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
A4. centrifugally washing the mixed solution obtained in the step 3 by using a tertiary butanol solution, centrifuging at 13000rpm for 10min, and taking a precipitate; and centrifuging at 10000rpm for 5min to obtain precipitate, repeating the steps for 3 times to obtain precipitate, drying at 80deg.C for 24 hr, and grinding for 10min until no obvious particles exist to obtain CsPbBr 1.5 I 1.5 Quantum dot @ COF-5 composite photocatalytic material.
Example 3
Example 3 CsPbI 3 The preparation method of the quantum dot@COF-5 composite photocatalytic material comprises the following steps:
A1. taking a COF-5 material, performing heat treatment at 120 ℃ for 72 hours, adopting acetone and dimethyl diamide to wash for many times, and grinding after vacuum drying to obtain COF-5 material powder;
A2. 400mg of the COF-5 material powder obtained in step A1 and 2mmol of PbI were weighed separately 2 After mixing, the mixture was dissolved in 30mL of Octadecene (ODE), and the mixture was stirred and heated to 120℃under argon atmosphere, and then 3mL of Oleic Acid (OA) and 3mL of Oleylamine Ligand (OLA) were addedPreserving heat for 1h until the mixture is completely dissolved;
A3. continuously heating the product obtained in the step 2 to 180 ℃, then rapidly injecting 1mL of 0.6mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
A4. centrifugally washing the mixed solution obtained in the step 3 by using a tertiary butanol solution, centrifuging for 5min at the rotating speed of 11000rpm, and taking precipitate; and then using the normal hexane solution with the rotating speed of 9000rpm, centrifuging for 5min to obtain precipitate, repeating the steps for 2 times to obtain precipitate, drying at 60 ℃ for 24h under vacuum, grinding for 10min until no particles exist, and obtaining CsPbI 3 Quantum dot @ COF-5 composite photocatalytic material.
Comparative example 1
The preparation method of the COF-5 material provided in the comparative example 1 comprises the following steps:
step B1, adding 0.4mmol, 0.6mmol, 10mL and 10mL of 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-benzene diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane under anhydrous and anaerobic environment, and adding 2,3,6,7,10, 11-hexahydroxy triphenyl and 1, 4-benzene diboronic acid into the mixed solution of 1,3, 5-trimethylbenzene and 1, 4-dioxane to form a mixture;
b2, sealing the mixture, performing ultrasonic dispersion, and oscillating to obtain uniform dispersion liquid;
b3, heating the dispersion liquid to a certain temperature, and reacting for a period of time;
and B4., washing a reaction product, then carrying out vacuum drying, finally introducing protective gas, and carrying out heat treatment on the product for a period of time at a set temperature to obtain the two-dimensional flaky COF-5 material.
Comparative example 2
CsPbBr provided in comparative example 2 3 The preparation method of the quantum dot comprises the following steps:
C1. weigh 1mmol PbBr 2 Dissolving in 20mL of Octadecene (ODE), uniformly mixing and stirring under argon atmosphere, heating to 100 ℃, then adding 1mL of Oleic Acid (OA) and 1mL of oleic acid ligand (OLA), and preserving heat for 1h until the mixture is completely dissolved;
C2. continuously heating the solution in the step 1 to 160 ℃, then rapidly injecting 1mL of 0.3mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
C3. centrifuging and washing the solution obtained in the step 2 by using a tertiary butanol solution, centrifuging at 10000rpm for 7min, and taking precipitate; and centrifuging at 8000rpm for 4min to obtain precipitate, repeating the steps for 2 times to obtain precipitate, drying at 60deg.C for 12 hr, and grinding for 5min until no obvious particles exist to obtain CsPbBr 3 Quantum dots.
Comparative example 3
CsPbBr provided in comparative example 3 1.5 I 1.5 The preparation method of the quantum dot comprises the following steps:
C1. 1.5mmol PbBr was weighed separately 2 、1.5mmol PbI 2 After mixing, dissolving in 30mL of Octadecene (ODE), uniformly mixing and stirring under argon atmosphere, heating to 120 ℃, then adding 2.5mL of Oleic Acid (OA) and 2.5mL of Oleylamine Ligand (OLA), and preserving heat for 1h until complete dissolution;
C2. continuously heating the solution in the step 1 to 170 ℃, then rapidly injecting 1mL of 0.5mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
C3. centrifuging and washing the mixed solution obtained in the step 2 by using a tertiary butanol solution, centrifuging for 10min at the rotating speed of 13000rpm, and taking a precipitate; and centrifuging at 10000rpm for 5min to obtain precipitate, repeating the steps for 3 times to obtain precipitate, drying at 80deg.C for 24 hr, and grinding for 10min until no obvious particles exist to obtain CsPbBr 1.5 I 1.5 Quantum dots.
Comparative example 4
CsPbI provided in comparative example 4 3 The preparation method of the quantum dot comprises the following steps:
C1. weigh 2mmol PbI 2 Dissolving in 30mL of Octadecene (ODE), stirring uniformly under argon atmosphere, heating to 120 ℃, adding 3mL of Oleic Acid (OA) and 3mL of Oleylamine Ligand (OLA), and preserving heat for 1h until complete dissolution;
C2. continuously heating the product obtained in the step 1 to 180 ℃, then rapidly injecting 1mL of 0.6mol/l cesium acetate solution, reacting for 5 seconds, and cooling to obtain a mixed solution;
C3. centrifuging and washing the mixed solution obtained in the step 2 by using a tertiary butanol solution, centrifuging for 5min at the rotation speed of 11000rpm to obtain precipitateThe method comprises the steps of carrying out a first treatment on the surface of the And then using the normal hexane solution with the rotating speed of 9000rpm, centrifuging for 5min to obtain precipitate, repeating the steps for 2 times to obtain precipitate, drying at 60 ℃ for 24h under vacuum, grinding for 10min until no particles exist, and obtaining CsPbI 3 Quantum dots.
COF-5 material prepared in comparative example 1 and CsPbBr prepared in comparative example 2 of the present invention 3 Quantum dots and CsPbBr prepared in example 1 3 The XRD pattern of the quantum dot@COF-5 composite photocatalytic material is shown in figure 1.XRD patterns show that the COF-5 material is successfully prepared by a solvothermal method; csPbBr was successfully prepared by thermal injection 3 A quantum dot; by in situ growth with CsPbBr 3 After the quantum dots are compounded, a diffraction peak of COF-5 still exists, and after the quantum dots are compounded, a new diffraction peak appears at 26.9 degrees, which corresponds to Pb 2 B 5 O 9 The (301) crystal plane of Br, csPbBr 3 After the quantum dots are compounded with the COF-5, new chemical bonds are formed.
CsPbBr prepared in comparative example 2 of the present invention 3 Quantum dot, csPbBr prepared in comparative example 3 1.5 I 1.5 Quantum dot, csPbI prepared in comparative example 4 3 The microscopic morphology of the quantum dots is shown in fig. 2. FIGS. 2 (a), 2 (b), and 2 (c) are PbBr, respectively 2 :PbI 2 The ratio is 3:0;1:1; csPbBr 0:3 3-x I x HRTEM image of Quantum dots, as can be seen from the figure, csPbBr prepared by thermal injection method 3-x I x The quantum dots have good dispersibility and no obvious agglomeration. Along with the gradual increase of the content of the I element, the sizes of the quantum dot particles are respectively 9.14nm, 9.20nm and 8.97nm, and the interplanar distances are respectively 0.282nm, 0.301nm and 0.316nm, which correspond to (002) crystal faces.
COF-5 material prepared in comparative example 1 and CsPbBr prepared in comparative example 2 of the present invention 3 Quantum dots and CsPbBr prepared in example 1 3 The UV-Vis spectrum of the quantum dot @ COF-5 composite photocatalytic material is shown in FIG. 3. The light absorption range of the COF-5 material is mainly concentrated in the ultraviolet light region, and the light absorption boundary is at 390 nm; csPbBr 3 The quantum dots have certain absorption in the ultraviolet light and visible light ranges, and the light absorption boundary is at 510 nm; csPbBr 3 After the quantum dots are compounded with the COF-5 material, the light response intensity is improved to a certain extent, and the light isThe absorption edge red shifted to 530nm.
COF-5 material prepared in comparative example 1, csPbI prepared in comparative example 4 of the present invention 3 Quantum dots and CsPbI prepared in example 3 3 The IR spectrum of the quantum dot @ COF-5 composite photocatalytic material is shown in figure 4.IR spectrum shows B-C, C-O, B-O bond at wavenumber 1010, 1241, 1348 nm; and CsPbI 3 After the quantum dots are compounded, long-chain C-C bonds exist at the wavenumbers 2852 and 2973nm, and the long-chain C-C bonds are surface ligands of the quantum dots.
COF-5 material prepared in comparative example 1 and CsPbBr prepared in comparative example 2 of the present invention 3 Quantum dots and CsPbBr prepared in example 1 3 CO of quantum dot@COF-5 composite photocatalytic material 2 The photocatalytic reduction efficiency curve is shown in fig. 5. FIG. 5 (a) and FIG. 5 (b) are the CO and CH under the action of UV-Vis light, respectively 4 Yield curve. From the figure, csPbBr 3 Quantum dot@COF-5 composite material as photocatalyst, CO 2 The reduction product is mainly CO, and the yield is far higher than that of pure CsPbBr 3 The quantum dot and COF-5 material are pure CsPbBr 3 The quantum dot is 11.9 times that of COF-5 material. In addition, the catalyst still has a certain CO under the action of Vis light 2 Photocatalytic reduction performance, efficiency curve is shown in FIG. 5 (c). Under the action of Vis light, csPbBr 3 CO of quantum dot@COF-5 composite material 2 The photocatalytic reduction product is CO, and the yield is pure CsPbBr 3 2.07 times of quantum dots.
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 (6)
1. CO reduction method for photocatalysis 2 CsPbBr of (A) 3-x I x The quantum dot@COF-5 composite photocatalytic material is characterized in that: csPbBr 3-x I x The quantum dots grow on the surface of the COF-5 material in situ,at the same time CsPbBr 3-x I x The quantum dots are connected with the COF-5 material through chemical bond cesium boron oxygen bonds Cs-B-O, and CsPbBr 3-x I x In the quantum dot, x is more than or equal to 0 and less than or equal to 3; the CsPbBr 3- x I x CsPbBr in quantum dot @ COF-5 composite photocatalytic material 3-x I x The mass percentage of the quantum dots is 20% -60%; the CsPbBr 3-x I x The quantum dot@COF-5 composite photocatalytic material forms an I-type heterojunction structure or an II-type heterojunction structure or an S-type heterojunction structure or a Z-type heterojunction structure; borate groups in COF-5 materials and CsPbBr 3-x I x Cesium ions Cs of quantum dots + Forming cesium boron oxygen Cs-B-O bond; the CsPbBr 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material comprises the following steps:
A1. taking the COF-5 material, washing, drying and grinding after heat treatment to obtain COF-5 material powder;
A2. respectively weighing the COF-5 material powder obtained in the step A1 and the Pb-containing precursor, mixing, dissolving in octadecene, uniformly mixing and heating in an inert gas atmosphere, adding oleic acid and oleic acid ligand, and keeping the temperature until the reaction is complete;
A3. continuously heating the product obtained in the step 2, then adding cesium acetate solution, reacting, and cooling to obtain a mixed solution;
A4. centrifuging, washing, drying and grinding the mixed solution obtained in the step 3 to obtain CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material;
the reaction precursor is PbBr 2 Or PbI 2 Or PbBr 2 And PbI 2 Wherein PbBr 2 ：PbI 2 The ratio of (3) to (n): n and n are in the range of 0.ltoreq.n.ltoreq.3.
2. A CsPbBr according to claim 1 3-x I x The quantum dot@COF-5 composite photocatalytic material is characterized in that: the COF-5 material is in a two-dimensional sheet structure.
3. According to the weightCsPbBr according to any of claims 1 to 2 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material is characterized by comprising the following steps of:
A1. taking the COF-5 material, washing, drying and grinding after heat treatment to obtain COF-5 material powder;
A2. respectively weighing the COF-5 material powder obtained in the step A1 and the Pb-containing precursor, mixing, dissolving in octadecene, uniformly mixing and heating in an inert gas atmosphere, adding oleic acid and oleic acid ligand, and keeping the temperature until the reaction is complete;
A3. continuously heating the product obtained in the step 2, then adding cesium acetate solution, reacting, and cooling to obtain a mixed solution;
A4. centrifuging, washing, drying and grinding the mixed solution obtained in the step 3 to obtain CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material;
the reaction precursor is PbBr 2 Or PbI 2 Or PbBr 2 And PbI 2 Wherein PbBr 2 ：PbI 2 The ratio of (3) to (n): n and n are in the range of 0.ltoreq.n.ltoreq.3.
4. A CsPbBr according to claim 3 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material is characterized by comprising the following steps of: in the step A2 and the step A3, the ratio of the COF-5 material powder, the Pb-containing precursor, the octadecene, the oleic acid ligand and the cesium acetate is 200-400mg:1-2mmol:10-30mL:1-3mL:1-3mL:0.3-0.6mmol.
5. A CsPbBr according to claim 3 3-x I x The preparation method of the quantum dot@COF-5 composite photocatalytic material is characterized by comprising the following steps of: in the step A1, the heat treatment temperature is 100-120 ℃, acetone and dimethyl diamide are adopted for washing for multiple times, in the step A2, the heating temperature and the heat preservation temperature are 100-120 ℃, in the step A3, the temperature is continuously raised to 160-180 ℃, in the step A4, tertiary butanol solution and n-hexane solution are adopted for alternately washing, the centrifugation time is 3-10min, the rotating speed is 8000-10000rpm, and the drying temperature is 8000-10000rpmGrinding at 60-80 ℃ until no obvious particles exist.
6. A CsPbBr according to any one of claims 1-2 3-x I x Quantum dot@COF-5 composite photocatalytic material or CsPbBr prepared by using preparation method of any one of claims 3-5 3-x I x Quantum dot@COF-5 composite photocatalytic material for efficiently reducing CO by photocatalysis 2 Is used in the field of applications.
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