CN114797979A - Porous photocatalyst and preparation method and application thereof - Google Patents
Porous photocatalyst and preparation method and application thereof Download PDFInfo
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- CN114797979A CN114797979A CN202210532820.XA CN202210532820A CN114797979A CN 114797979 A CN114797979 A CN 114797979A CN 202210532820 A CN202210532820 A CN 202210532820A CN 114797979 A CN114797979 A CN 114797979A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 90
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 238000007146 photocatalysis Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 24
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- 238000002390 rotary evaporation Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
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- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 2
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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
- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01J35/61—Surface area
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Abstract
The invention relates to a porous photocatalyst and a preparation method and application thereof, belonging to the field of photocatalytic materials. The porous photocatalyst provided by the invention comprises a photocatalytic monomer and a hydrogen bond acceptor functional molecule. The porous photocatalyst formed by the recognition and assembly of the host and the guest between the photocatalytic monomer and the hydrogen bond receptor functional molecule has ultrahigh chemical stability and catalytic activity, and has wide application prospect in the field of photocatalysis.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a porous photocatalyst as well as a preparation method and application thereof.
Background
Photocatalysis is an environment-friendly green treatment technology, and generates active substances with strong oxidation function by utilizing abundant light resources in the nature. The photocatalysis technology is not only suitable for various oxidation catalytic reactions, but also can degrade and mineralize harmful organic pollutants in water and air, and thoroughly solves the problem of environmental harm caused by the pollutants. Therefore, there has been much interest in developing photocatalysts having high catalytic activity.
The photocatalytic performance is closely related to the size of the catalyst, and the nano-scale catalyst structure has excellent catalytic efficiency. However, the catalyst with a micro size brings high surface activity, agglomeration of the catalyst is easily generated in a repeated reaction process, so that the quenching and deactivation of the catalyst are caused, and the application of the photocatalyst is severely limited. The porous catalyst structure can effectively prevent aggregation among catalysts, and the multi-dimensional and multi-scale pore channels of the porous catalyst structure are suitable for rapid transfer of active substances, so that effective collision of chemical reactions is promoted, and the porous catalyst structure is an optional way for improving catalytic conversion times and conversion frequency.
Although the porous composite photocatalyst is successfully designed and synthesized by successfully doping photocatalytic elements in porous channels through various physical or chemical technologies, experimental results show that the performance of the composite material is not obviously improved and the ideal catalytic effect is far from being achieved. For example, supporting a photosensitive catalyst on a porous surface increases the surface energy of the catalyst, which tends to cause deactivation of the catalyst during the reaction. On the other hand, the catalyst is doped in the pore channel framework, so that the size and the shape of the pore channel cannot be guaranteed, and the problem of pore channel blockage is easily caused in the using process. It is hopeful to form one-, two-or molecular-state photocatalysts on the pore surface if the interaction between the catalysts is destroyed by an additional strong external field.
The supermolecule organic porous frames (SOFS) constructed based on the hydrogen bonding of organic molecules are novel porous ordered crystals, have light weight and low toxicity, and can adsorb volatile gas and aromatic organic pollutant particles more quantitatively. Compared with other porous crystals, the SOFs structure can be regulated and controlled by utilizing the structures of corresponding hydrogen bond hosts and objects and the external environment, and then the porous material is selectively prepared through the processes of molecular recognition and assembly. Therefore, how to further prepare porous SOFs photocatalysts with high catalytic activity and high stability is a technical problem to be solved by current research.
Disclosure of Invention
The present invention aims to overcome the problems in the prior art and provide a porous photocatalyst, a preparation method and an application thereof.
The invention is realized by the following technical scheme:
the invention provides a porous photocatalyst, which comprises a photocatalytic monomer and a hydrogen bond receptor functional molecule; the molecular structure of the photocatalytic monomer is shown as a formula (1), and the molecular structure of the hydrogen bond receptor functional molecule is shown as a formula (2);
the porous photocatalyst provided by the invention is formed by assembling a photocatalytic monomer and a hydrogen bond acceptor functional molecule together; the photocatalytic monomer is a benzene triamide derivative with one end bonded with a photocatalytic element, and the other two ends of amide are connected with pyridine, so that a hydrogen bond driven supermolecule self-assembly structure can be formed. The hydrogen bond receptor functional molecule is C3 symmetric benzene triamide derivative, all amides are bonded with pyridine, and the pyridine as the hydrogen bond receptor can perform hydrogen bond recognition with the amide bonded with the photocatalytic element by the monomer to prevent the agglomeration quenching of the photocatalytic element. By means of host and guest recognition and assembly between the photocatalytic monomer and the hydrogen bond acceptor functional molecules, the formed porous structure is beneficial to preventing agglomeration between the photocatalytic monomers, is beneficial to rapid transfer of photoactive substances and improves photocatalytic efficiency. Experimental results show that the constructed porous photocatalyst has ultrahigh chemical stability and catalytic activity, and has wide application prospects in the field of photocatalysis.
As a preferred embodiment of the porous photocatalyst of the present invention, the molar ratio of the photocatalytic monomer to the hydrogen bond acceptor functional molecule is 1: (1-5).
Preferably, the molar ratio of the photocatalytic monomer to the hydrogen bond acceptor functional molecule is 1:1 and 1: 5.
another object of the present invention is to provide a method for preparing the porous photocatalyst, comprising the steps of:
s1, stirring substrate dithienyl-pyrrolopyrrole-dione, bromo-isooctane and potassium tert-butoxide in a solvent a, and carrying out rotary evaporation and purification to obtain an intermediate A; stirring the obtained intermediate A, Boc-bromoethylamine and potassium tert-butoxide in a solvent a, and performing rotary evaporation and purification to obtain an intermediate B; stirring the obtained intermediate B and trifluoroacetic acid in a solvent B in an ice-water bath, performing rotary evaporation, and purifying to obtain a photocatalytic element;
s2, stirring trimesic acid, 2-aminomethyl pyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, and performing rotary evaporation and purification to obtain an intermediate C; stirring the obtained intermediate C, the obtained photocatalytic element, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation, and purifying to obtain a photocatalytic monomer;
s3, stirring, rotary steaming and purifying trimesic acid, 2-aminomethyl pyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a to obtain a hydrogen bond receptor functional molecule;
and S4, respectively dissolving the obtained photocatalytic monomer and functional molecules in acetone, mixing the two, and performing rotary evaporation to obtain the photocatalytic monomer.
As a preferred embodiment of the method for preparing the porous photocatalyst of the present invention, in the step S1, the solvent a is N, N-dimethylformamide; the solvent b is dichloromethane; the stirring time is 3-7 h.
Preferably, in the step S1, the stirring time is 3h to 6 h.
In a preferred embodiment of the method for preparing the porous photocatalyst of the present invention, in step S1, the molar ratio of the substrate to the bromoisooctane is 1 (1-2); the molar ratio of the intermediate A to Boc-bromoethylamine is 1 (1-2).
Preferably, in the step S1, the molar ratio of the substrate to the bromoisooctane is 1: 1; the molar ratio of the intermediate A to Boc-bromoethylamine is 1: 1.
In a preferred embodiment of the method for preparing the porous photocatalyst of the present invention, in step S2, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (2 to 3), the molar ratio of intermediate C to photocatalytic unit is 1 (1 to 2), and the stirring time is 5 to 7 hours.
Preferably, in the step S2, the molar ratio of the trimesic acid to the 2-aminomethyl pyridine is 1: 2; the molar ratio of the intermediate C to the photocatalytic unit is 1: 1; the stirring time is 6 h.
In a preferred embodiment of the method for preparing a porous photocatalyst of the present invention, in step S3, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (3 to 4); the stirring time is 5-7 h.
Preferably, in the step S3, the molar ratio of the trimesic acid to the 2-aminomethyl pyridine is 1: 3; the stirring time is 6 h.
As a preferred embodiment of the preparation method of the porous photocatalyst of the present invention, in steps S1, S2 and S3, column chromatography is used for the purification, and an eluent of the column chromatography is at least one of methanol and dichloromethane. Preferably, the mixed solvent of methanol and dichloromethane is selected in different proportions according to the polarity of the product.
In a preferred embodiment of the method for preparing the porous photocatalyst of the present invention, in step S4, the photocatalytic monomer and the hydrogen bond acceptor functional molecule are mixed in a molar ratio of 1 (1-5). Preferably, in the step S4, the photocatalytic monomer and the hydrogen bond acceptor functional molecule are mixed in a molar ratio of 1:1 or 1: 5. The invention respectively prepares a photocatalytic monomer and a hydrogen bond receptor functional molecule with respective acetone solution to form a self-assembly aggregation structure, wherein both the two molecules form a layered hydrogen bond framework, two sides of the hydrogen bond framework of the photocatalytic monomer are provided with photocatalytic elements, and two sides of the hydrogen bond framework of the hydrogen bond receptor functional molecule are provided with hydrogen bond receptor pyridine. And mixing the two solutions according to the molar ratio of 1 (1-5) to construct the porous photocatalyst. The strategy based on supramolecular recognition and assembly can effectively enhance the stability of a pore channel structure in the porous photocatalyst and has a good active oxygen mass transfer function.
Still another object of the present invention is to apply the porous photocatalyst and the method for preparing the porous photocatalyst of the present invention to photocatalysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention constructs a pore channel and inhibits the agglomeration of photocatalytic elements based on firm supermolecule recognition and assembly functions, effectively improves the photoresponse characteristic, and generates strong hydrogen bond recognition function between a photocatalytic monomer and functional molecules, wherein the porous photocatalyst formed by co-assembly of two proportions of 1:1 and 1:5 has firm pore unit structure, is beneficial to the effective transmission of active oxygen, and shows excellent photoresponse activity.
(2) The porous photocatalyst disclosed by the invention has extremely strong stability, has long-term catalytic activity, is a pore channel formed based on hydrogen bond supermolecule assembly, has good structural stability, and is not easy to collapse. Under long-term illumination, the catalytic performance of the porous catalyst is still maintained, and the porous catalyst has long-term stability and has obvious advantages in practical catalytic application.
(3) The porous photocatalyst shows extremely high catalytic conversion rate in catalytic oxidation of aldehydes and degradation of pollutants, has super-strong photocatalytic activity, and has wide application prospect in the fields of catalytic conversion and pollutant degradation.
Drawings
FIG. 1 shows NMR spectra of photocatalytic monomer(s) (( 1 H-NMR chart, nuclear magnetic resonance carbon spectrum (C: ( 13 C-NMR) and time-of-flight mass spectrometry (MALDI-TOF MS);
FIG. 2 is a schematic structural diagram of a photocatalytic monomer, the porous photocatalysts of example 1 and example 2;
FIG. 3(a) is a nitrogen adsorption/desorption curve of the porous photocatalyst of example 1, (b) example 2;
FIG. 4 is an X-ray diffraction pattern of a photocatalytic monomer, the porous photocatalysts of example 1 and example 2;
FIG. 5(a) is a UV spectrum of a photocatalytic monomer, the porous photocatalysts of example 1 and example 2, and FIG. 5(b) is a fluorescence spectrum of a photocatalytic monomer, the porous photocatalysts of example 1 and example 2;
FIG. 6 is a plot of the rate of singlet oxygen generation for the photocatalytic monomer, the porous photocatalysts of example 1 and example 2;
FIG. 7 is a stability test chart of a photocatalytic monomer, the porous photocatalysts of example 1 and example 2;
FIG. 8 is a graph showing the conversion of benzaldehyde by the photocatalytic monomer, the porous photocatalyst of example 1 and example 2;
fig. 9 is a graph of the rate of catalytic degradation of methyl orange by a photocatalytic monomer, the porous photocatalyst of example 1 and example 2;
wherein, in FIGS. 4-9, 1 is a photocatalytic monomer; 1:1 is the porous photocatalyst of example 1; 1: and 5 is the porous photocatalyst of example 2.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
Example 1
Synthesizing a photocatalytic monomer: dispersing 2.4g (8mmol) of photosensitizer thienyl-pyrrolopyrroledione in 100mL of N, N-dimethylformamide, adding 0.9g (8mmol) of potassium tert-butoxide, stirring for 10 minutes, adding 1.54g (8mmol) of bromo-isooctane, continuing to stir for 7 hours, stopping the reaction, removing the N, N-dimethylformamide by rotary evaporation, purifying by column chromatography, and eluting by dichloromethane to obtain 1.2g of isooctane substituted thienyl-pyrrolopyrroledione intermediate A.
Taking 1.2g (2.9mmol) of intermediate A, dispersing the intermediate in 50mL of N, N-dimethylformamide, adding 0.33g (2.9mmol) of potassium tert-butoxide, stirring for 10 minutes, adding 0.65g (2.9mmol) of Boc-bromoethylamine, continuing to stir for 6 hours, stopping the reaction, removing the N, N-dimethylformamide by rotary evaporation, purifying by column chromatography, and eluting with pure dichloromethane to obtain 0.61g of isooctane and Boc substituted thienyl-pyrrolopyrroledione intermediate B.
0.61g of intermediate B (1.1mmol) is taken and dispersed in 100mL of dichloromethane, ice-water bath is carried out for 10 minutes, 20mL of trifluoroacetic acid is added, the reaction is stopped after the stirring is continued for 3 hours, the trifluoroacetic acid and the dichloromethane are removed by rotary evaporation, column chromatography is used for purification, and pure dichloromethane is used for elution, so as to obtain 0.46g of amino-substituted thienyl-pyrrolo-pyrrole-dione photocatalysis element.
0.5g of trimesic acid (2.4mmol) and 0.52g (4.8mmol) of 3-aminomethyl pyridine are uniformly dispersed in 30mLN, N-dimethylformamide, 0.62g of N, N-diisopropylethylamine (4.8mmol) is added, after stirring for 10 minutes, 1.82g of benzotriazoltetramethylurea hexafluorophosphate (4.8mmol) is added, after stirring for 6 hours, the reaction is stopped, N-dimethylformamide is removed by rotary evaporation, purification is carried out by column chromatography, and elution is carried out by a dichloromethane-methanol mixed solvent with a volume ratio of 5:1, so as to obtain 0.43g of intermediate C with amidation at both ends.
Dispersing 0.40g of intermediate C (1.02mmol) in 40mL of N, N-dimethylformamide, adding 0.46g of photocatalytic element (1.02mmol) and 0.13g of 0.13g N, N-diisopropylethylamine (1.02mmol), stirring for 10 minutes, adding 0.39g of benzotriazoltetramethylurea hexafluorophosphate (1.02mmol), continuing stirring, tracking the reaction progress by using a Thin Layer Chromatography (TLC) dot plate, stopping the reaction after 6 hours, removing N, N-dimethylformamide by rotary evaporation, purifying by using column chromatography, and adding dichloromethane at a volume ratio of 10: 1: eluting with methanol mixed solvent, separating and purifying with high performance liquid chromatography column to obtain 0.58g of photocatalytic monomer with yield of 69%.
Synthesis of hydrogen bond receptor functional molecules: 0.5g of trimesic acid (2.4mmol) and 0.78g (7.2mmol) of 3-aminomethyl pyridine are uniformly dispersed in 30mL of N, N-dimethylformamide, 0.93g N, N-diisopropylethylamine (7.2mmol) is added, after stirring for 10 minutes, 2.73g of benzotriazoltetramethylurea hexafluorophosphate (7.2mmol) is added, after stirring for 6 hours, the reaction is stopped, N-dimethylformamide is removed by rotary evaporation, purification is carried out by column chromatography, and elution is carried out by a dichloromethane-methanol mixed solvent with the volume ratio of 10:1, so as to obtain 1.1g of hydrogen bond receptor functional molecule.
And (3) respectively and ultrasonically dispersing the prepared photocatalytic functional monomer and hydrogen bond receptor functional molecules in acetone uniformly, and preparing a mixed solution according to a molar ratio of 1:1 to obtain a mixed solution of 1:1, an assembled porous photocatalyst.
Example 2
The preparation method of the photocatalytic functional monomer and the hydrogen bond receptor functional molecule is the same as that in the embodiment 1, the prepared photocatalytic functional monomer and the hydrogen bond receptor functional molecule are respectively and uniformly dispersed in acetone in an ultrasonic mode, and the molar ratio is 1:5 preparing a mixed solution, namely 1:5 assembled porous photocatalyst.
Example 3
The preparation method of the photocatalytic functional monomer and the hydrogen bond receptor functional molecule is the same as that in the embodiment 1, the prepared photocatalytic functional monomer and the hydrogen bond receptor functional molecule are respectively and uniformly dispersed in acetone in an ultrasonic mode, and the molar ratio is 1:2 preparing a mixed solution, namely 1:2, and 2, assembling the porous photocatalyst.
Example 4
The preparation method of the photocatalytic functional monomer and the hydrogen bond receptor functional molecule is the same as that in the embodiment 1, the prepared photocatalytic functional monomer and the hydrogen bond receptor functional molecule are respectively and uniformly dispersed in acetone in an ultrasonic mode, and the molar ratio is 1:3 preparing a mixed solution to obtain a mixed solution of 1:3, and (3) assembling the porous photocatalyst.
Example 5
The preparation method of the photocatalytic functional monomer and the hydrogen bond receptor functional molecule is the same as that in the embodiment 1, the prepared photocatalytic functional monomer and the hydrogen bond receptor functional molecule are respectively and uniformly dispersed in acetone in an ultrasonic mode, and the molar ratio is 1: 4 preparing a mixed solution, namely 1: 4, and 4, assembling the porous photocatalyst.
Application example 1
The nuclear magnetic resonance hydrogen spectrum, carbon spectrum and flight time mass spectrum of the prepared photocatalytic monomer are shown in figure 1, and the specific data are as follows: 1 H-NMR(400MHz,D6-DMSO,δ,ppm)9.31(t,J＝5.9Hz,2H),8.96(t,J＝5.9Hz,1H),8.71(d,J＝3.7Hz,2H),8.68(d,J＝4.0Hz,2H),8.58(s,2H),8.47(d,J＝4.8Hz,2H),8.46(s,1H),8.39(s,2H),8.06(d,J＝4.9Hz,2H),8.01(d,J＝4.9Hz,2H),7.74(d,J＝9.9Hz,2H),7.34-7.36(m,4H),4.51(d,J＝5.9Hz,4H),4.23(t,J＝6.4Hz,2H),3.94(m,2H),3.59(q,J＝6.2Hz,2H),1.72(m,1H),1.23(m,8H),0.80(m,6H)； 13 C NMR(100MHz,D6-DMSO,δ,ppm)166.2,166.0,161.3,161.2,149.4,148.6,140.1,134.0,135.8,135.3,135.3,135.0,135.0,134.6,133.1,133.0,129.6,129.5,129.3,129.0,129.0,128.9,124.0,107.4,107.4,45.4,41.8,41.1,39.1,38.9,30.0,28.1,23.4,22.9,14.3,10.7；MALDI-TOF mass:m/z calculated for C 45 H 45 N 7 O 5 S 2 [M+H] + ,828.29；found:[M+H] + ,828.30。
the specific data of the nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the flight time mass spectrum of the prepared hydrogen bond receptor functional molecule are as follows: 1 H-NMR(400MHz,D6-DMSO,δ,ppm)9.34(t,J＝5.9Hz,3H),8.54(d,J＝2.2Hz,3H),8.45(s,3H),8.44(d,J＝5.8Hz,3H),7.75(d,J＝7.9Hz,3H),7.37(dd,J＝7.8,4.8Hz,3H),4.51(d,J＝5.8Hz,6H)； 13 C-NMR(100MHz,D6-DMSO,δ,ppm)166.0,149.4,148.6,135.7,135.3,135.2,129.3 124.0,41.1；MALDI TOF mass:m/z calculated for C 27 H 24 N 6 O 3 [M+H] + ,481.19；found:[M+H] + ,481.18。
the prepared supramolecular assembly porous photocatalyst is characterized by X-ray diffraction, fig. 2 is a schematic structural diagram of a photocatalytic monomer and the porous photocatalysts of examples 1 and 2, fig. 3 is a nitrogen adsorption and desorption curve of the porous photocatalysts of examples 1 and 2, and fig. 4 is an X-ray diffraction diagram of the photocatalytic monomer and the porous photocatalysts of examples 1 and 2. As can be seen from fig. 2, 3 and 4, 1 of embodiment 1:1 the assembled porous photocatalyst shows a layer-by-layer assembled structure, and the specific surface area of the photocatalyst is 18.3m 2 And/g, formed by alternately stacking layered assemblies of photocatalytic monomers and functional molecules, and generating channels between layers. Example 2 1:5 the assembled porous photocatalyst shows hexagonal shapeOrdered structure with a specific surface area of 31.3m 2 And/g, honeycomb-shaped pore channels are formed in the structure. The porous channel structure formed in the porous catalyst can prevent the agglomeration of the photocatalytic monomers, is favorable for the rapid transfer of an optical active substance, and improves the photocatalytic efficiency.
Ultraviolet visible spectrum and fluorescence spectrum tests are carried out on the photocatalytic monomer and the porous photocatalysts in the embodiments 1 and 2 through an ultraviolet visible spectrum spectrometer and a fluorescence spectrometer, and the results are shown in fig. 5, wherein the photocatalytic monomer shows a quenched fluorescence state in an acetone solution, and the light responsiveness is poor; 1 of example 1:1, the assembled porous photocatalyst presents a J-shaped aggregate state, and the photoresponse is greatly improved; example 2 preparation of 1: the spectrum of the 5-assembled porous photocatalyst shows a molecular state and has the best photoresponse.
The photocatalytic monomer and two kinds of porous photocatalysts of example 1 and example 2 are subjected to active oxygen generation rate test, the molar concentration of the catalyst is 0.1mM, the singlet oxygen probe concentration is 0.1mM, 520nm monochromatic light is used as an excitation light source, the active oxygen generation rate result is shown in fig. 6, the photocatalytic monomer consumes 60s of all singlet oxygen probes, and the active oxygen generation rate test of example 1 is as follows: 1-assembled porous photocatalyst was used only for 24s, while example 2 1:5 the assembled photocatalyst is increased to 18s, which shows that the hole structure of the porous photocatalyst based on supramolecular recognition and assembly can effectively enhance the generation rate of active oxygen.
And comparing the rate of the degraded singlet oxygen probe after continuous illumination with an initial value to determine the structural stability of the assembled photocatalyst. As shown in FIG. 7, the catalytic efficiency of the photocatalytic monomer after 4h of light irradiation was only 38% of that of the initial state, while the catalytic efficiencies of the porous photocatalysts of example 1 and example 2 were 75% and 91%, respectively, indicating that the porous photocatalyst of the present invention has excellent light irradiation stability.
Application example 2
When the photocatalytic monomer, the porous photocatalysts of example 1 and example 2 are used for catalytic oxidation reaction of benzaldehyde, the molar concentration of the catalyst is 0.1mM, the concentration of the benzaldehyde is 0.1M, the catalytic conversion rate is determined under AM1.5G simulated solar illumination, the test result is shown in figure 8, after 4 hours of catalytic reaction, the photocatalytic monomer only converts 50% of catalytic substrate, and the conversion rate of the porous photocatalysts of example 1 and example 2 exceeds 90%, and extremely high catalytic activity is shown. And, during the first 1 hour of catalytic reaction, example 1's 1:1 the conversion of the assembled porous photocatalyst was 28%, example 2 1:5 the catalytic conversion rate of the assembled porous photocatalyst is 52 percent, which shows that the honeycomb-shaped porous structure has stronger catalytic conversion frequency.
The photocatalytic monomer, the porous photocatalyst of example 1 and example 2 were used for the degradation of methyl orange, the concentration of methyl orange was 50mg/L, the concentration of the catalyst was 0.1mM, and the rate of photodegradation was measured under AM1.5G simulated solar illumination. The test result is shown in fig. 9, the photocatalytic monomer only degrades 23% at 60 minutes, and the two porous photocatalysts of example 1 and example 2 degrade 91% and 96% of pollutants respectively, and show extremely strong photocatalytic degradation activity. Experimental results show that the porous photocatalyst based on molecular recognition and assembly has super-strong photocatalytic activity in applications such as photocatalytic conversion and pollutant degradation, and has a wide application prospect in the field of photocatalysis.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A porous photocatalyst is characterized by comprising a photocatalytic monomer and a hydrogen bond acceptor functional molecule; the molecular structure of the photocatalytic monomer is shown as a formula (1), and the molecular structure of the hydrogen bond receptor functional molecule is shown as a formula (2);
2. the porous photocatalyst according to claim 1, wherein the molar ratio of the photocatalytic monomer to the hydrogen bond acceptor functional molecule is 1: (1-5).
3. A method for preparing the porous photocatalyst of claim 1, comprising the steps of:
s1, stirring substrate dithienyl-pyrrolopyrrole-dione, bromo-isooctane and potassium tert-butoxide in a solvent a, and carrying out rotary evaporation and purification to obtain an intermediate A; stirring the obtained intermediate A, Boc-bromoethylamine and potassium tert-butoxide in a solvent a, and performing rotary evaporation and purification to obtain an intermediate B; stirring the obtained intermediate B and trifluoroacetic acid in a solvent B in an ice-water bath, performing rotary evaporation, and purifying to obtain a photocatalytic element;
s2, stirring trimesic acid, 2-aminomethyl pyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, and performing rotary evaporation and purification to obtain an intermediate C; stirring the obtained intermediate C, the obtained photocatalytic element, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation, and purifying to obtain a photocatalytic monomer;
s3, stirring, rotary steaming and purifying trimesic acid, 2-aminomethyl pyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a to obtain a hydrogen bond receptor functional molecule;
and S4, respectively dissolving the obtained photocatalytic monomer and functional molecules in acetone, mixing the two, and performing rotary evaporation to obtain the photocatalytic monomer.
4. The method for preparing a porous photocatalyst according to claim 3, wherein in step S1, the solvent a is N, N-dimethylformamide; the solvent b is dichloromethane; the stirring time is 3-7 h.
5. The method for preparing the porous photocatalyst according to claim 3, wherein in the step S1, the molar ratio of the substrate to the bromoisooctane is 1 (1-2); the molar ratio of the intermediate A to Boc-bromoethylamine is 1 (1-2).
6. The method for preparing the porous photocatalyst according to claim 3, wherein in the step S2, the molar ratio of the trimesic acid to the 2-aminomethylpyridine is 1 (2-3), the molar ratio of the intermediate C to the photocatalytic unit is 1 (1-2), and the stirring time is 5h-7 h.
7. The method for preparing the porous photocatalyst according to claim 3, wherein in the step S3, the molar ratio of the trimesic acid to the 2-aminomethylpyridine is 1 (3-4); the stirring time is 5-7 h.
8. The method for preparing the porous photocatalyst according to claim 3, wherein in the steps S1, S2 and S3, column chromatography is adopted for the purification, and an eluent of the column chromatography is at least one of methanol and dichloromethane.
9. The preparation method of the porous photocatalyst according to claim 3, wherein in the step S4, the photocatalytic monomer and the hydrogen bond acceptor functional molecule are mixed in a molar ratio of 1 (1-5).
10. Use of the porous photocatalyst according to claim 1 or 2, the method of preparation according to any one of claims 3 to 9 in photocatalysis.
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