CN115318340A - CsPbBr 3 Ligand regulation method and application of perovskite nano particles - Google Patents
CsPbBr 3 Ligand regulation method and application of perovskite nano particles Download PDFInfo
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 25
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention belongs to the technical field of catalytic surface interface and photocatalyst preparation, and discloses CsPbBr 3 A ligand regulation method and application of perovskite nano particles, namely preparing an oleylamine surface ligand, a lead bromide precursor solution, an oleic acid surface ligand and a cesium carbonate precursor solution; rapidly injecting an oleic acid surface ligand and cesium carbonate precursor liquid into an oleylamine surface ligand and a lead bromide precursor liquid for reaction, cooling in an ice bath, and stopping the reaction; regulating and controlling the quantity of the ligand on the surface of the catalyst by repeatedly washing toluene and acetone; drying under the continuous vacuum-pumping state to prepare ligand regulated CsPbBr 3 A perovskite nanoparticle photocatalyst. CsPbBr containing a large amount of surface oleylamine ligand 3 The performance of the perovskite nano-particle photocatalyst for photocatalytic reduction of carbon dioxide is CsPbBr containing a small amount of surface oleylamine ligand 3 1.93 times of perovskite nano-particle photocatalyst, greatly improves CsPbBr 3 Activity of perovskite nanoparticle photocatalyst.
Description
Technical Field
The present invention belongs to a catalytic watchThe technical field of interface and photocatalyst preparation, in particular to CsPbBr 3 A ligand regulation method of perovskite nano particles and application thereof.
Background
At present, the increasingly severe problems of environmental pollution and energy shortage faced by today's society can be solved by using sustainable clean solar energy to purify environmental pollution and convert solar energy into chemical energy. The photocatalyst can directly utilize sunlight or artificial light, and has received wide attention from people in terms of representing huge application potential in the fields of environmental protection, material science and solar energy conversion. Under the drive of sunlight, the photocatalysis material can catalyze carbon dioxide to be converted into renewable energy under mild reaction conditions, so that the carbon recycling is realized, and the method is a major subject of scientific workers. In the development process of the technology for converting carbon dioxide by photocatalysis, the photocatalysis material is the most important one, and in the last decades, researchers have been dedicated to research and develop novel, controllable, high-activity and good-stability photocatalysts.
As a new photoelectron semiconductor material, the perovskite nano particle material has large band gap adjustability, effective narrow-band emission, low cost and easy synthesis; has excellent optical and electrical properties and has wide application prospect in the field of electro-optics, thereby attracting the attention of the whole world. However, functional studies on organic ligands on the surfaces of perovskite nanoparticles are lacked, and the surface organic ligands form a coordination interface with the surfaces of perovskite nanoparticle photocatalysts, so that the catalytic reaction process is deeply influenced. Therefore, revealing the action mechanism and nature of the surface organic ligand influencing the photocatalytic performance is a potential application bottleneck of the perovskite nano-particles.
While CsPbBr 3 Perovskite nano particles are used as a novel photocatalyst applied to photocatalytic reduction of carbon dioxide, and due to the surface and interface effect, small-size effect and quantum effect of nano particle materials, the perovskite nano particles exist in a monodispersed form in the catalysis process, and the perovskite nano particles are not aggregated or have many defects to cause the reduction of catalytic activity and other excellent characteristics to be paid extensive attention. At the same timeExploring CsPbBr 3 The evolution mechanism of the organic ligand on the surface of the perovskite nano particle and the influence mechanism of the organic ligand on the catalytic process have important theoretical value and scientific significance in the fields of catalytic chemistry, surface interface, catalyst design and the like.
Through the above analysis, the problems and defects of the prior art are as follows: the existing specific technical scheme aiming at functional analysis and ligand modification of organic ligands on the surfaces of perovskite nano particles in photocatalytic application is not reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides CsPbBr 3 A ligand regulation method and application of perovskite nano particles, in particular to a ligand regulation CsPbBr based on a thermal injection method 3 Perovskite nano-particle photocatalyst, preparation method and application thereof in reducing carbon dioxide.
The invention is realized by that a ligand-regulated CsPbBr 3 Perovskite nanoparticle photocatalyst, the ligand regulating CsPbBr 3 The perovskite nano-particle photocatalyst takes halogen perovskite nano-particles as an inorganic core, and an organic surface ligand shell layer is wrapped outside the perovskite nano-particles.
Further, the halogen perovskite nano-particle is CsPbBr 3 。
Further, the CsPbBr 3 The organic ligand species on the surface of the perovskite nano-particle are oleic acid and oleylamine, and the surface organic ligand oleylamine is coated on CsPbBr 3 Perovskite nanoparticle surface.
Further, the CsPbBr 3 The number of organic ligands on the surface of the perovskite nanoparticles is different.
Another objective of the invention is to provide a method for implementing the ligand regulation CsPbBr 3 Ligand regulation CsPbBr of perovskite nanoparticle photocatalyst 3 Preparation method of perovskite nanoparticle photocatalyst, and ligand regulation CsPbBr 3 The preparation method of the perovskite nanoparticle photocatalyst comprises the following steps:
preparing an oleylamine surface ligand and a lead bromide precursor solution; preparing an oleic acid surface ligand and a cesium carbonate precursor solution; mixing oleic acid tableRapidly injecting the surface ligand and cesium carbonate precursor solution into the oleylamine surface ligand and lead bromide precursor solution for reaction, cooling in an ice bath, and stopping the reaction; regulating and controlling the quantity of the surface ligand of the catalyst by the exchange washing of toluene and acetone; drying under the continuous vacuum-pumping state to prepare ligand-regulated CsPbBr 3 A perovskite nanoparticle photocatalyst.
Further, the temperature of the precursor is 150-200 ℃, and the drying temperature is 60-100 ℃.
Further, the ligand regulates CsPbBr 3 The preparation method of the perovskite nanoparticle photocatalyst comprises the following steps:
dissolving lead bromide in octadecene, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1h; adding oleylamine and oleic acid surface ligand, heating to 150 ℃ until the solid is completely dissolved, and generating precursor solution containing the surface ligand and lead bromide;
dissolving cesium carbonate in octadecene, adding an oleic acid ligand, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1h to completely dissolve the cesium carbonate to generate an oleic acid-containing surface ligand and a cesium carbonate precursor solution;
step three, quickly injecting the cesium carbonate precursor solution obtained in the step two into the oleylamine surface ligand and lead bromide precursor solution obtained in the step one, and reacting for 5s; rapidly cooling to room temperature through ice bath, and stopping the reaction;
step four, centrifuging the solution obtained in the step three in a centrifuge to obtain a lower-layer solid; adding toluene into the lower-layer solid, fully dissolving, adding a certain amount of acetone, separating out the solid, and centrifuging in a centrifuge to obtain the lower-layer solid; repeating the operation for 2 times to obtain CsPbBr with a large number of surface ligands 3 Perovskite nanoparticles; repeating the operation for 2 times again to obtain CsPbBr with small amount of surface ligand 3 Perovskite nanoparticles; regulating and controlling the quantity of the surface ligands of the catalyst by repeatedly washing toluene and acetone to obtain CsPbBr with different quantities of surface ligands 3 A perovskite nanoparticle photocatalyst;
step five, the lower layer solid obtained in the step four is put into a vacuum oven for drying, and the vacuum ovenPlacing in a fume hood, and maintaining vacuum state to obtain CsPbBr with different surface ligands 3 A perovskite nanoparticle photocatalyst.
Further, the centrifugation condition is 10000 revolutions per minute and 5min;
the drying condition is drying for 12 hours at the temperature of 80 ℃.
Another purpose of the invention is to provide the ligand-regulated CsPbBr 3 Application of perovskite nanoparticle photocatalyst in photocatalytic carbon dioxide reduction.
In combination with the above technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with the technical scheme to be protected and the results and data in the research and development process, and some creative technical effects brought after the problems are solved are analyzed in detail and deeply. The specific description is as follows:
the CsPbBr provided by the invention 3 The quantity of the ligands on the surface of the perovskite nano-particle can be regulated, a hydrophobic microenvironment can be formed on the surface of the nano-particle through the surface ligands, and the surface ligands can enrich carbon dioxide in CsPbBr 3 The activity of the perovskite nano particle surface for photocatalytic carbon dioxide reduction is greatly improved.
The experimental result can prove that the CsPbBr with more surface ligands 3 Perovskite nanoparticles and CsPbBr with reduced surface ligand quantity 3 The activities of the perovskite nano particles for photocatalytic reduction of carbon dioxide are obviously different, and the activities of the perovskite nano particles for photocatalytic reduction of carbon dioxide are obviously improved.
The invention discloses a ligand regulation CsPbBr based on a thermal injection method 3 The preparation method of the perovskite nano-particle photocatalyst is applied to carbon dioxide reduction, and CsPbBr is regulated and controlled by a simple method 3 The quantity of the ligand on the surface of the perovskite nano-particles is such that the surface shape of the perovskite nano-particlesForming a hydrophobic microenvironment, promoting the enrichment of carbon dioxide on the surface and improving the catalytic activity of the photocatalytic reduction of carbon dioxide.
Secondly, considering the technical scheme as a whole or from the perspective of products, the technical effect and advantages of the technical scheme to be protected by the invention are specifically described as follows:
the catalyst provided by the invention improves the activity of photocatalytic carbon dioxide reduction by regulating the quantity of organic ligands on the surface of perovskite nano particles, and proves that CsPbBr 3 The change of the number of the ligands on the surface of the perovskite nano-particles can effectively regulate and control the reduction performance of the photocatalytic carbon dioxide.
The CsPbBr containing a large amount of surface oleylamine ligands provided by the invention 3 The performance of the perovskite nano-particle photocatalyst in the photocatalytic reduction of carbon dioxide is CsPbBr containing a small amount of surface oleylamine ligand 3 1.93 times of perovskite nano-particle photocatalyst, greatly improves CsPbBr 3 Activity of perovskite nanoparticle photocatalyst.
Third, as inventive supplementary proof of the claims of the present invention, there are several important aspects as follows:
the technical scheme of the invention overcomes the technical prejudice whether: different from the method for exchanging the ligand after the synthesis of the perovskite nanoparticle surface ligand, the invention regulates and controls CsPbBr by the simplest method through the washing process in the synthesis 3 The number of the ligands on the surface of the perovskite nano particle enables the surface of the perovskite nano particle to form a hydrophobic microenvironment and effectively regulates and controls the reduction performance of the photocatalytic carbon dioxide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows CsPbBr according to an embodiment of the present invention 3 Ligand modulation of perovskite nanoparticlesA method flow diagram;
FIG. 2 shows the ligand-regulated CsPbBr according to the present invention 3 A flow chart of a preparation method of the perovskite nanoparticle photocatalyst;
FIG. 3 shows CsPbBr with a larger number of surface ligands, provided in examples 1 and 2 of the present invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 XRD patterns of perovskite nanoparticle photocatalysts (XRD is an abbreviation of X-ray Diffraction, i.e. X-ray Diffraction);
FIG. 4 shows CsPbBr with a larger number of surface ligands, provided in examples 1 and 2 of the present invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with less surface ligand quantity 3 FT-IR plot of perovskite nanoparticle photocatalyst;
FIG. 5 shows CsPbBr with larger amount of surface ligands provided in example 1 of the present invention 3 A TEM image of the perovskite nanoparticle photocatalyst;
FIG. 6 shows CsPbBr with a larger number of surface ligands provided in example 2 of the present invention 3 TEM images of perovskite nanoparticle photocatalysts;
FIG. 7 shows CsPbBr with a larger number of surface ligands, provided in examples 1 and 2 of the present invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 PL plot of perovskite nanoparticle photocatalyst;
FIG. 8 shows CsPbBr with a larger number of surface ligands, provided in examples 1 and 2 of the present invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 A UV-Vis DRS diagram of the perovskite nanoparticle photocatalyst;
FIG. 9 shows CsPbBr with a larger number of surface ligands, provided in examples 1 and 2 of the present invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 A comparison graph of activities of perovskite nanoparticle photocatalysts in reducing carbon dioxide;
FIG. 10 shows CsPbBr with larger amount of surface ligands provided in example 1 of the present invention 3 An In-situ FT-IR diagram during reduction of carbon dioxide by the perovskite nanoparticle photocatalyst;
FIG. 11 is a surface provided in example 2 of the present inventionCsPbBr with reduced ligand content 3 An In-situ FT-IR diagram during reduction of carbon dioxide by the perovskite nanoparticle photocatalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Aiming at the problems in the prior art, the invention provides CsPbBr 3 The invention relates to a ligand regulation method and application of perovskite nano particles, which are described in detail in the following by combining accompanying drawings.
As shown in fig. 1, csPbBr provided by the embodiment of the present invention 3 The ligand regulation method of the perovskite nano-particles comprises the following steps:
s101, preparing an oleylamine surface ligand and a lead bromide precursor solution;
s102, preparing an oleic acid surface ligand and cesium carbonate precursor solution;
s103, quickly injecting the oleic acid surface ligand prepared in the S102 and cesium carbonate precursor liquid into the oleylamine surface ligand prepared in the S101 and lead bromide precursor liquid for reaction, cooling in ice bath, and stopping the reaction;
s104, repeatedly washing by exchanging toluene and acetone to regulate and control the number of ligands on the surface of the catalyst; drying under the continuous vacuum-pumping state to prepare ligand-regulated CsPbBr 3 A perovskite nanoparticle photocatalyst.
As a preferred embodiment, as shown in fig. 2, the CsPbBr provided in the embodiment of the present invention 3 The ligand regulation and control method of the perovskite nano particles specifically comprises the following steps:
s1, lead bromide (PbBr) 2 ) Dissolving in Octadecylene (ODE), heating to 120 ℃ under the protection of argon, keeping the temperature unchanged for 1 hour, adding oleylamine and oleic acid surface ligand, heating to 150 ℃ until the solid is completely dissolved, and generating a precursor solution containing the surface ligand and lead bromide;
s2, adding cesium carbonate (CsCO) 3 ) Dissolving in Octadecene (ODE), adding oleic acid ligand, dissolving in water, addingHeating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1 hour to completely dissolve cesium carbonate to generate an oleic acid-containing surface ligand and a cesium carbonate precursor solution;
s3, quickly injecting the cesium carbonate precursor solution obtained in the S2 into the oleylamine surface ligand and lead bromide precursor solution obtained in the S1, reacting for 5S, quickly cooling to room temperature through ice bath, and stopping the reaction;
and S4, centrifuging the solution obtained in the step S3 in a centrifuge at 10000 rpm for 5 minutes to obtain a lower-layer solid. And adding toluene into the lower layer solid to fully dissolve the lower layer solid, adding a certain amount of acetone to separate out the solid, and centrifuging the solid in a centrifuge at 10000 rpm for 5 minutes to obtain the lower layer solid. Repeating the above operation for 2 times to obtain CsPbBr with large amount of surface ligands 3 Perovskite nanoparticles. Repeating the above operation for 2 times to obtain CsPbBr with small amount of surface ligand 3 Perovskite nanoparticles. Regulating and controlling the quantity of the surface ligands of the catalyst by repeatedly washing toluene and acetone to obtain CsPbBr with different quantities of surface ligands 3 A perovskite nanoparticle photocatalyst;
s5, putting the lower-layer solid obtained in the step S4 into a vacuum oven, and drying for 12 hours at the temperature of 80 ℃ (the vacuum oven is placed in a fume hood and is kept in a vacuumizing state all the time), so that CsPbBr with different surface ligands can be obtained 3 A perovskite nanoparticle photocatalyst.
Ligand regulation CsPbBr prepared by the embodiment of the invention 3 The perovskite nano-particle photocatalyst is characterized, and the ligand regulation CsPbBr can be known 3 The perovskite nanoparticle photocatalyst has the following characteristics:
CsPbBr with large amount of surface ligands 3 Perovskite nanoparticle photocatalyst and CsPbBr with less surface ligand quantity 3 XRD analysis of the perovskite nanoparticle photocatalyst, as shown in fig. 3; csPbBr synthesized by thermal injection method 3 The perovskite nanoparticles have complete CsPbBr 3 Crystal structure, number variation of surface ligands to CsPbBr 3 The crystal structure of the perovskite nano particles is not changed at all.
As shown in FIG. 4, are surface ligandsLarge amount of CsPbBr 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 FT-IR (FT-IR is an abbreviation for Fourier-Transform Infrared Spectroscopy) of perovskite nanoparticle photocatalyst, from which a characteristic surface ligand vibrational peak (-CH) was detected 3 ，-C＝C-，-N-H，-CH 2 ，-CH 3 -CH) and a higher amount of surface ligands CsPbBr was detected 3 The characteristic vibration peak intensity of the ligand on the surface of the perovskite nano particle is obviously stronger than that of CsPbBr with more ligands 3 Perovskite nanoparticles, p CsPbBr 3 The number of the ligands on the surface of the perovskite nano-particles is visually detected.
As shown in FIG. 5, csPbBr was present in a large amount as a surface ligand 3 TEM image of perovskite nanoparticle photocatalyst (TEM is an abbreviation of Transmission Electron Microscope), and CsPbBr is found 3 The average diameter of the perovskite nano-particle catalyst is 9.05nm, csPbBr 3 The perovskite nanoparticle catalyst has lattice stripes of
And CsPbBr 3 The (1 0) crystal face of the PDF standard card in XRD is coincided, thereby proving that CsPbBr is 3 The perovskite nanoparticle catalyst is successfully synthesized.
As shown in FIG. 6, csPbBr was present in a small amount as a surface ligand 3 TEM image of perovskite nanoparticle photocatalyst (TEM is an abbreviation of High Resolution Transmission Electron Microscope), csPbBr 3 The average particle size of the perovskite nanoparticle catalyst is 16.84nm, and CsPbBr with different surface ligand quantity is found 3 The perovskite nano particle catalyst has no obvious difference in morphology, and CsPbBr with small amount of surface ligand 3 Perovskite nano-particles and CsPbBr with large amount of surface ligands 3 Compared with the perovskite nano particle catalyst, the particle size is increased, and the quantity of the surface ligands is less CsPbBr 3 The direct spacing of the perovskite nanoparticle grains becomes smaller, and connection recombination partially occurs.
Regulation of CsPbBr to ligands 3 PL test (PL is abbreviation of Photolutence, i.e. fluorescence spectrum) of perovskite nanoparticle photocatalyst was performed, and as shown in FIG. 7, the result indicates that CsPbBr is present in a large amount with surface ligands 3 Compared with the perovskite nano-particle photocatalyst, the PL intensity is obviously reduced along with the reduction of the number of the surface ligands, and obvious red shift occurs, which is caused by the space confinement effect of the surface ligands, so that CsPbBr 3 The recombination rate of the photon-generated carriers of the perovskite nano-particle photocatalyst is obviously reduced.
Regulation of CsPbBr to ligands 3 The perovskite nanoparticle photocatalyst is subjected to UV-Vis DRS analysis (UV-Vis DRS is UV-Visible dispersion spectrum, namely ultraviolet-Visible diffuse reflection), as shown in FIG. 8, the photoresponse range is tested, and the absorption capacity of the perovskite nanoparticle photocatalyst with a large number of surface ligands to light is increased, and meanwhile, the light absorption range is widened. This is because the steric hindrance reduces the degree of quantum confinement due to a change in the steric structure of the surface ligands.
CsPbBr with larger amount of surface ligands provided by the embodiment of the invention through the amount of products generated by photocatalytic reduction of carbon dioxide 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 The catalytic performance of the perovskite nanoparticle photocatalyst was tested. The test procedure was as follows:
10mg of CsPbBr with a larger amount of surface ligand prepared by the embodiment of the invention 3 Perovskite nanoparticle photocatalyst or CsPbBr with less surface ligand 3 Uniformly dispersing the perovskite nano-particle photocatalyst in a small amount of toluene solution, performing ultrasonic treatment for 5 minutes to fully dissolve a sample in toluene, uniformly coating the mixed solution on a glass fiber membrane with the radius of 2.0cm and the pore diameter of 0.25 mu m, putting the coated glass fiber membrane into a vacuum oven, and continuously vacuumizing for 24 hours at 60 ℃ to remove the redundant toluene on the glass fiber membrane.
Carrying out photocatalytic reduction on carbon dioxide in a reactor of a Labsolar-6A closed circulation system, maintaining the temperature of the reactor at 20 ℃ by adopting a circulating cooling system, vacuumizing the reaction system, blowing pure carbon dioxide through a gas cylinder, repeatedly vacuumizing, blowing pure carbon dioxide for three times, and finally maintaining carbon dioxide with about 1 atmospheric pressure in the reactor. The photocatalytic reduction of the carbon dioxide product was quantitatively analyzed by a GC2002 gas chromatograph using a 300W xenon lamp as a light source.
CsPbBr with more surface ligands provided by the embodiment of the invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with less surface ligand quantity 3 The photocatalytic reduction carbon dioxide activity of perovskite nanoparticles is shown in FIG. 9, in which CsPbBr with a large number of surface ligands is present 3 The perovskite nano-particle photocatalyst has the highest activity, and 206 mu mol g of carbon dioxide is generated by reducing carbon dioxide after 5 hours of illumination -1 With a reduced amount of surface ligands CsPbBr 3 Compared with perovskite nano particles, the activity is improved by 1.93 times.
As shown in FIGS. 10 to 11, csPbBr was added to the surface ligands in a large amount 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 In-situ FT-IR Spectroscopy (In-situ Fourier-Transform Spectroscopy) of perovskite nanoparticle photocatalyst with high surface ligand quantity of CsPbBr 3 Intermediate species generated by perovskite nanoparticle photocatalyst in the catalysis process are remarkably stronger than CsPbBr with more surface ligands 3 The perovskite nano-particle photocatalyst proves that the activity of photocatalytic carbon dioxide reduction is remarkably improved due to a large number of surface ligands, the strong combination of intermediate species generated on the surface can weaken the chemical bond on the surface, the migration of surface atoms is easily caused, and the ligands are in CsPbBr 3 The perovskite nano particle surface promotes carbon dioxide catalytic reaction.
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
The CsPbBr with more surface ligands provided by the embodiment of the invention 3 The preparation method of the perovskite nano-particle photocatalyst specifically comprises the following steps:
s1, dissolving 207mg of lead bromide in 15mL of octadecene, heating to 120 ℃ under the protection of argon, keeping the temperature unchanged for 1 hour, adding 1.5mL of oleylamine and 1.5mL of oleic acid serving as surface ligands, heating to 150 ℃ until the solids are completely dissolved, and generating the oleylamine-containing surface ligand and lead bromide precursor solution.
S2, dissolving 27mg of cesium carbonate in 1mL of octadecene, adding 0.2mL of oleic acid serving as a surface ligand, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1 hour to completely dissolve the cesium carbonate to generate an oleic acid-containing surface ligand and a cesium carbonate precursor solution.
And S3, quickly injecting the cesium carbonate precursor into the S1, reacting for 5 seconds, quickly cooling to room temperature through an ice bath, and stopping the reaction.
And S4, centrifuging the mixture in a centrifuge at 10000 rpm for 5 minutes to obtain lower-layer solid. Adding 10mL of toluene into the lower layer solid to fully dissolve the lower layer solid, then adding 30mL of acetone to separate out the solid, centrifuging the solid in a centrifuge at 10000 rpm for 5 minutes to obtain the lower layer solid, and repeatedly washing and centrifuging the lower layer solid for 2 times. Regulating and controlling the amount of the surface ligands of the catalyst by washing toluene and acetone for a few times to obtain CsPbBr with a large amount of surface ligands 3 A perovskite nanoparticle photocatalyst.
S5, putting the lower-layer solid obtained in the last time into a vacuum oven, drying for 12 hours at the temperature of 80 ℃ (the vacuum oven is placed in a fume hood and is kept in a vacuumizing state all the time), and obtaining the CsPbBr with a large number of surface ligands 3 A perovskite nanoparticle photocatalyst.
Example 2
The CsPbBr with less surface ligands provided by the embodiment of the invention 3 The preparation method of the perovskite nano-particle photocatalyst specifically comprises the following steps:
s1, dissolving 207mg of lead bromide in 15mL of octadecene, heating to 120 ℃ under the protection of argon, keeping the temperature unchanged for 1 hour, adding 1.5mL of oleylamine and 1.5mL of oleic acid serving as surface ligands, heating to 150 ℃ until the solids are completely dissolved, and generating the oleylamine-containing surface ligand and lead bromide precursor solution.
S2, dissolving 27mg of cesium carbonate in 1mL of octadecene, adding 0.2mL of oleic acid serving as a surface ligand, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1 hour to completely dissolve the cesium carbonate to generate an oleic acid-containing surface ligand and a cesium carbonate precursor solution.
And S3, quickly injecting the cesium carbonate precursor into the S1, reacting for 5 seconds, quickly cooling to room temperature through an ice bath, and stopping the reaction.
And S4, centrifuging the mixture in a centrifuge at 10000 rpm for 5 minutes to obtain lower-layer solid. Adding 10mL of toluene into the lower layer solid to fully dissolve the lower layer solid, then adding 30mL of acetone to separate out the solid, centrifuging the solid in a centrifuge at 10000 rpm for 5 minutes to obtain the lower layer solid, and repeatedly washing and centrifuging the lower layer solid for 4 times. The quantity of the ligands on the surface of the catalyst is regulated and controlled by washing toluene and acetone for multiple times to obtain CsPbBr with less surface ligands 3 A perovskite nanoparticle photocatalyst.
S5, putting the lower-layer solid obtained in the last time into a vacuum oven, drying for 12 hours at the temperature of 80 ℃ (the vacuum oven is placed in a fume hood and is kept in a vacuumizing state all the time), and thus CsPbBr with a small number of surface ligands can be obtained 3 A perovskite nanoparticle photocatalyst.
CsPbBr with larger amount of surface ligands prepared by the examples provided in examples 1 and 2 of the invention 3 Perovskite nanoparticle photocatalyst and CsPbBr with small amount of surface ligand 3 The perovskite nano-particle photocatalyst is used for carrying out photocatalytic reduction on carbon dioxide, wherein CsPbBr with more surface ligands is adopted 3 The perovskite nano-particle photocatalyst has high activity, and can reduce carbon dioxide to generate 206 mu mol g after 5 hours of illumination -1 With a reduced amount of surface ligands CsPbBr 3 Illumination of the perovskite nanoparticles for 5 hours produced 107. Mu. Mol g -1 Compared with carbon monoxide, the activity is improved by 1.93 times.
From the above examples, it can be demonstrated that CsPbBr is present in a large amount in the surface ligand 3 Perovskite nanoparticles and CsPbBr with reduced surface ligand quantity 3 The activities of the perovskite nano particles for photocatalytic reduction of carbon dioxide are obviously different, and the activities of the perovskite nano particles for photocatalytic reduction of carbon dioxide are obviously improved.
The invention discloses a ligand regulation CsPbBr based on a thermal injection method 3 The preparation method of the perovskite nano-particle photocatalyst is applied to carbon dioxide reduction, and CsPbBr is regulated and controlled by a simple method 3 The quantity of the ligands on the surface of the perovskite nano particles enables the surface of the perovskite nano particles to form a hydrophobic microenvironment, promotes the enrichment of carbon dioxide on the surface, and improves the catalytic activity of the photocatalytic reduction of the carbon dioxide.
It is noted that the preparation of ligand-regulated CsPbBr provided by the embodiments of the present invention 3 The preparation method of the perovskite nanoparticle photocatalyst has universality, so that the person skilled in the art can make various similar numbers without departing from the spirit and the claims of the invention under the teaching of the invention, and the changes are all within the protection scope of the invention.
The embodiment of the invention discloses a ligand regulation CsPbBr based on a thermal injection method 3 The preparation method of the perovskite nano-particle photocatalyst is applied to carbon dioxide reduction, and CsPbBr is regulated and controlled by a simple method 3 The quantity of the ligands on the surface of the perovskite nano particles enables the surface of the perovskite nano particles to form a hydrophobic microenvironment, promotes the enrichment of carbon dioxide on the surface, and improves the catalytic activity of the photocatalytic reduction of the carbon dioxide.
CsPbBr with large number of surface ligands 3 The perovskite nano-particle photocatalyst has high activity, and can reduce carbon dioxide to generate 206 mu mol g after 5 hours of illumination -1 With a reduced amount of surface ligands CsPbBr 3 Illumination of the perovskite nanoparticles for 5 hours produced 107. Mu. Mol g -1 Compared with carbon monoxide, the activity is improved by 1.93 times.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention disclosed in the present invention should be covered within the scope of the present invention.
Claims (10)
1. Ligand regulation CsPbBr 3 Perovskite nanoparticle photocatalyst, characterized in that the ligand-regulated CsPbBr 3 The perovskite nano-particle photocatalyst takes halogen perovskite nano-particles as an inorganic core, and an organic surface ligand shell layer is wrapped outside the perovskite nano-particles.
2. The ligand-modulated CsPbBr of claim 1 3 The perovskite nano-particle photocatalyst is characterized in that the halogen perovskite nano-particle is CsPbBr 3 。
3. The ligand-regulated CsPbBr of claim 1 3 Perovskite nanoparticle photocatalyst, characterized in that the CsPbBr is 3 The organic ligand species on the surface of the perovskite nano-particle are oleic acid and oleylamine, and the surface organic ligand oleylamine is coated on CsPbBr 3 Perovskite nanoparticle surface.
4. The ligand-regulated CsPbBr of claim 1 3 Perovskite nanoparticle photocatalyst, characterized in that the CsPbBr is 3 The number of organic ligands on the surface of the perovskite nano-particles is different.
5. A method for implementing the ligand modulation CsPbBr according to any one of claims 1 to 4 3 Ligand regulation CsPbBr of perovskite nanoparticle photocatalyst 3 The preparation method of the perovskite nano-particle photocatalyst is characterized in that the ligand is used for regulating CsPbBr 3 The preparation method of the perovskite nanoparticle photocatalyst comprises the following steps:
preparing an oleylamine surface ligand and a lead bromide precursor solution; preparing an oleic acid surface ligand and a cesium carbonate precursor solution; rapidly injecting an oleic acid surface ligand and cesium carbonate precursor liquid into an oleylamine surface ligand and lead bromide precursor liquid for reaction, cooling in an ice bath, and stopping the reaction; regulating and controlling the number of ligands on the surface of the catalyst by repeatedly washing toluene and acetone; drying under the continuous vacuum-pumping state to prepare ligand regulated CsPbBr 3 A perovskite nanoparticle photocatalyst.
6. The ligand-regulated CsPbBr of claim 5 3 The preparation method of the perovskite nano-particle photocatalyst is characterized in that the temperature of the precursor is 150-200 ℃, and the drying temperature is 60-100 ℃.
7. The ligand-regulated CsPbBr of claim 5 3 The preparation method of the perovskite nanoparticle photocatalyst is characterized in that the cesium ions are selected from any one of cesium carbonates.
8. The ligand-regulated CsPbBr of claim 5 3 The preparation method of the perovskite nanoparticle photocatalyst is characterized in that the ligand is used for regulating CsPbBr 3 The preparation method of the perovskite nano-particle photocatalyst comprises the following steps:
dissolving lead bromide in octadecene, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1h; adding oleylamine and oleic acid surface ligand, heating to 150 ℃ until the solid is completely dissolved, and generating precursor solution containing the surface ligand and lead bromide;
dissolving cesium carbonate in octadecene, adding an oleic acid ligand, heating to 120 ℃ under the protection of argon, and keeping the temperature unchanged for 1h to completely dissolve the cesium carbonate to generate an oleic acid-containing surface ligand and a cesium carbonate precursor solution;
step three, quickly injecting the cesium carbonate precursor solution obtained in the step two into the oleylamine surface ligand and lead bromide precursor solution obtained in the step one, and reacting for 5s; rapidly cooling to room temperature through ice bath, and stopping the reaction;
step four, centrifuging the solution obtained in the step three in a centrifugal machine to obtain lower-layer solid; adding toluene into the lower-layer solid, fully dissolving, adding a certain amount of acetone, separating out the solid, and centrifuging in a centrifuge to obtain the lower-layer solid; repeating the operation for 2 times to obtain CsPbBr with a large number of surface ligands 3 Perovskite nanoparticles; repeating the operation for 2 times again to obtain CsPbBr with small amount of surface ligands 3 Perovskite nanoparticles; regulating and controlling the number of ligands on the surface of the catalyst by repeatedly washing toluene and acetone to obtain the tableCsPbBr with different number of face ligands 3 A perovskite nanoparticle photocatalyst;
step five, putting the lower-layer solid obtained in the step four into a vacuum oven for drying, putting the vacuum oven into a fume hood, and keeping the vacuum oven in a vacuumizing state all the time to obtain CsPbBr with different surface ligands 3 A perovskite nanoparticle photocatalyst.
9. The ligand-modulated CsPbBr of claim 8 3 The preparation method of the perovskite nanoparticle photocatalyst is characterized in that the centrifugation condition is 10000 revolutions per minute and 5 minutes;
the drying condition is drying for 12 hours at the temperature of 80 ℃.
10. The ligand-regulated CsPbBr according to any one of claims 1 to 4 3 Application of perovskite nanoparticle photocatalyst in photocatalytic carbon dioxide reduction.
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