CN114797979B - Porous photocatalyst and preparation method and application thereof - Google Patents
Porous photocatalyst and preparation method and application thereof Download PDFInfo
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- 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 62
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- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
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- 239000000758 substrate Substances 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 4
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- 238000006731 degradation reaction Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical group CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
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- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 1
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B01J35/56—
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- B01J35/613—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to a porous photocatalyst, a preparation method and application thereof, and belongs 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 utilizing the recognition and assembly of the host and the guest between the photocatalytic monomer and the hydrogen bond acceptor 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, and a preparation method and application thereof.
Background
Photocatalysis is an environment-friendly green treatment technology, which utilizes abundant light resources in nature to generate active substances with strong oxidation function. 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 hazard caused by pollutants. Therefore, development of a photocatalyst having high catalytic activity has been attracting attention.
Wherein, the photocatalysis performance is closely related to the size of the catalyst, and the nano-scale catalyst structure has excellent catalysis efficiency. However, the micro-sized catalyst brings high surface activity, agglomeration of the catalyst is easy to generate in the repeated reaction process, so that the catalyst is quenched and deactivated, and the application of the photocatalyst is severely limited. The porous catalyst structure can not only effectively prevent aggregation among catalysts, but also ensure that multidimensional and multi-scale pore channels are suitable for rapid transmission of active substances, promote effective collision of chemical reactions, and are alternative ways for improving catalytic conversion times and conversion frequency.
Although the porous composite photocatalyst is successfully designed and synthesized by doping the photocatalytic element in the porous pore canal 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, loading a photoactive catalyst onto a porous surface increases the surface energy of the catalyst, which can easily cause deactivation of the catalyst during the reaction. On the other hand, the catalyst is doped in the pore canal framework, so that the size and shape of the pore canal cannot be ensured, and the problem of blocking of the pore canal is easily caused in the use process. The formation of one-dimensional, two-dimensional or molecular photocatalysts at the pore surface is hopefully achieved if the interaction between the catalysts is disrupted by an additional stronger external field.
Supermolecular organic porous frameworks (SOFs) constructed based on hydrogen bonding of organic molecules are novel porous ordered crystals, are light in weight and low in toxicity, and can more quantitatively adsorb volatile gases and aromatic organic pollutant particles. Compared with other porous crystals, the SOFs structure can be regulated and controlled by utilizing the structures of corresponding hydrogen bond hosts and guests and the external environment, and further the porous material is selectively prepared through the molecular recognition and assembly process. Therefore, how to further prepare porous SOFs photocatalysts with high catalytic activity and high stability is a technical problem to be solved in the current research.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a porous photocatalyst, a preparation method and 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 acceptor functional molecule; the molecular structure of the photocatalytic monomer is shown as a formula (1), and the molecular structure of the hydrogen bond acceptor functional molecule is shown as a formula (2);
the porous photocatalyst provided by the invention is formed by co-assembling a photocatalytic monomer and a hydrogen bond acceptor functional molecule; the photocatalytic monomer is a benzene triamide derivative with one end bonded with a photocatalytic element, and the other two ends are amide-connected with pyridine, so that a supermolecule self-assembly structure driven by hydrogen bonds can be formed. The hydrogen bond acceptor functional molecule is a benzene triamide derivative with C3 symmetry, all amides are bonded with pyridine, and the pyridine can be used as a hydrogen bond acceptor to be hydrogen-bonded with the amide of the monomer bonded photocatalysis unit so as to prevent the aggregation quenching of the photocatalysis unit. The porous structure formed by the host and guest recognition and assembly between the photocatalytic monomers and the hydrogen bond acceptor functional molecules is beneficial to preventing agglomeration among the photocatalytic monomers, facilitating rapid transfer of photoactive substances and improving photocatalytic efficiency. Experimental results show that the constructed porous photocatalyst has ultrahigh chemical stability and catalytic activity and has wide application prospect 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 substrates dithienyl-pyrrolopyrrole dione, bromoisooctane and potassium tert-butoxide in a solvent a, performing rotary evaporation and purification to obtain an intermediate A; stirring the obtained intermediate A, boc-bromoethylamine and potassium tert-butoxide in a solvent a, steaming in a rotary way, and purifying to obtain an intermediate B; stirring the obtained intermediate B and trifluoroacetic acid in an ice water bath in a solvent B, steaming in a rotary way, and purifying to obtain a photocatalysis element;
s2, stirring trimesic acid, 2-aminomethylpyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation, and purifying 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 purification to obtain a photocatalytic monomer;
s3, stirring trimesic acid, 2-aminomethylpyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation and purification to obtain a hydrogen bond acceptor functional molecule;
s4, respectively dissolving the obtained photocatalytic monomer and functional molecule in acetone, and then mixing the photocatalytic monomer and the functional molecule, and performing rotary evaporation to obtain the photocatalyst.
As a preferred embodiment of the method for preparing a 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 6h.
As a preferred embodiment of the method for preparing a porous photocatalyst of the present invention, in the step S1, the molar ratio of the substrate to bromoisooctane is 1 (1-2); the mol ratio of the intermediate A to Boc-bromoethylamine is 1 (1-2).
Preferably, in the step S1, the molar ratio of the substrate to bromoisooctane is 1:1; the molar ratio of the intermediate A to the Boc-bromoethylamine is 1:1.
As a preferred embodiment of the preparation method of the porous photocatalyst, in the step S2, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (2-3), the molar ratio of the intermediate C to the photocatalytic element is 1 (1-2), and the stirring time is 5-7 h.
Preferably, in the step S2, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1:2; the molar ratio of the intermediate C to the photocatalytic element is 1:1; the stirring time is 6h.
As a preferred embodiment of the method for preparing a porous photocatalyst of the present invention, in the step S3, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (3-4); the stirring time is 5-7 h.
Preferably, in the step S3, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1:3; the stirring time is 6h.
In the preferred embodiment of the method for preparing a porous photocatalyst according to the present invention, in each of the steps S1, S2 and S3, a 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 with different proportions is selected according to the polarity of the product.
As a preferred embodiment of the method for preparing a porous photocatalyst according to the present invention, in the step S4, a photocatalytic monomer and a hydrogen bond acceptor functional molecule are mixed in a molar ratio of 1 (1 to 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. According to the invention, the photocatalytic monomer and the hydrogen bond acceptor functional molecule are respectively configured with respective acetone solution to form a self-assembled aggregation structure, the two molecules form layered hydrogen bond frameworks, photocatalytic elements are arranged at two sides of the hydrogen bond framework of the photocatalytic monomer, and hydrogen bond acceptor pyridine is arranged at two sides of the hydrogen bond framework of the hydrogen bond acceptor functional molecule. And mixing the two solutions according to a molar ratio of 1 (1) - (5), thereby constructing the porous photocatalyst. The strategy based on supermolecule recognition and assembly can effectively enhance the stability of the pore channel structure in the porous photocatalyst, and has a good active oxygen mass transfer function.
It is still another object of the present invention to apply the porous photocatalyst of the present invention and the method for producing the porous photocatalyst to photocatalysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) The porous photocatalyst formed by co-assembling the photocatalytic monomer and the functional molecule in the ratio of 1:1 and 1:5 has a firm pore unit structure, is favorable for effective transmission of active oxygen, and shows excellent light response activity.
(2) The porous photocatalyst provided by the invention has extremely strong stability, long-term catalytic activity, and good structural stability and difficult collapse, and is based on a pore canal formed by the hydrogen bond supermolecule assembly effect. The porous catalyst of the invention has the advantages of maintained catalytic performance, long-term stability and remarkable advantages in practical catalytic application under long-time illumination.
(3) The porous photocatalyst provided by the invention has extremely high catalytic conversion rate in the catalytic oxidation of aldehydes and degradation of pollutants, has super-strong photocatalytic activity, and has wide application prospects in the fields of catalytic conversion and pollutant degradation.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectrum of photocatalytic monomer 1 H-NMR) chart and nuclear magnetic resonance carbon spectrum 13 C-NMR) and time-of-flight mass spectrometry (MALDI-TOF MS) maps;
FIG. 2 is a schematic structural diagram of a photocatalytic monomer, a porous photocatalyst of example 1 and example 2;
FIG. 3 (a) is a graph showing the adsorption and desorption of nitrogen from the porous photocatalyst of example 1 (b) of example 2;
FIG. 4 is an X-ray diffraction pattern of the photocatalytic monomer, the porous photocatalyst of example 1 and example 2;
FIG. 5 (a) is an ultraviolet spectrum of the porous photocatalyst of the photocatalytic monomer, example 1 and example 2, and FIG. 5 (b) is a fluorescence spectrum of the porous photocatalyst of the photocatalytic monomer, example 1 and example 2;
FIG. 6 is a graph of the rate of singlet oxygen production by the photocatalytic monomer, the porous photocatalyst of example 1 and example 2;
FIG. 7 is a graph of stability tests of photocatalytic monomers, porous photocatalysts of examples 1 and 2;
FIG. 8 is a graph showing the conversion rate of benzaldehyde by catalytic oxidation with a photocatalytic monomer, a porous photocatalyst of example 1 and example 2;
FIG. 9 is a graph of the rate at which the photocatalytic monomer, the porous photocatalyst of example 1 and example 2 catalyzes the degradation of methyl orange;
in fig. 4 to 9, 1 is a photocatalytic monomer; 1:1 is the porous photocatalyst of example 1; 1:5 is the porous photocatalyst of example 2.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
Example 1
Synthesizing a photocatalytic monomer: 2.4g (8 mmol) of photosensitizer thienyl-pyrrolopyrrole diketone is taken and dispersed in 100mL of N, N-dimethylformamide, 0.9g (8 mmol) of potassium tert-butoxide is added, after stirring for 10 minutes, 1.54g (8 mmol) of bromoisooctane is added, the reaction is stopped after stirring for 7 hours, N-dimethylformamide is removed by rotary evaporation, purification is carried out by using column chromatography, and dichloromethane is used for eluting, thus obtaining 1.2g of isooctane substituted thienyl-pyrrolopyrrole diketone intermediate A.
Intermediate A1.2g (2.9 mmol) was dispersed in 50mL of N, N-dimethylformamide, 0.33g (2.9 mmol) of potassium tert-butoxide was added, and after stirring for 10 minutes, 0.65g (2.9 mmol) of Boc-bromoethylamine was added, and after stirring was continued for 6 hours, the reaction was stopped, N-dimethylformamide was removed by rotary evaporation, purification was performed by column chromatography, eluting with pure dichloromethane, to give 0.61g of isooctane, boc-substituted thienyl-pyrrolopyrrolidone intermediate B.
0.61g of intermediate B (1.1 mmol) was taken and dispersed in 100mL of methylene chloride, and the mixture was subjected to ice-water bath for 10 minutes, and then 20mL of trifluoroacetic acid was added, followed by stopping the reaction after stirring for 3 hours, and the trifluoroacetic acid and methylene chloride were removed by rotary evaporation, and purification was carried out by column chromatography, eluting with pure methylene chloride, to obtain 0.46g of amino-substituted thienyl-pyrrolopyrroldiketone photocatalytic moiety.
0.5g of trimesic acid (2.4 mmol) and 0.52g (4.8 mmol) of 3-aminomethylpyridine were uniformly dispersed in 30mLN, N-dimethylformamide, 0.62g of N, N-diisopropylethylamine (4.8 mmol) was added, and after stirring for 10 minutes, 1.82g of benzotriazole tetramethylurea hexafluorophosphate (4.8 mmol) was added, and after stirring was continued for 6 hours, the reaction was stopped, N-dimethylformamide was removed by rotary evaporation, purification was performed by column chromatography, and elution was performed with a mixed solvent of methylene chloride: methanol at a volume ratio of 5:1, to obtain 0.43g of intermediate C having both ends amidated.
0.40g of intermediate C (1.02 mmol) was dispersed in 40mL of N, N-dimethylformamide, 0.46g of the photocatalytic unit (1.02 mmol) and 0.13g of N, N-diisopropylethylamine (1.02 mmol) were added, stirring was continued for 10 minutes, 0.39g of benzotriazol tetramethylurea hexafluorophosphate (1.02 mmol) was added, the progress of the reaction was followed by a Thin Layer Chromatography (TLC) plate, the reaction was stopped after 6 hours, and N, N-dimethylformamide was removed by rotary evaporation, purification was carried out using column chromatography with methylene chloride in a volume ratio of 10:1: eluting with methanol mixed solvent, separating and purifying with high performance liquid chromatography column to obtain 0.58g photocatalytic monomer with 69% yield.
Synthesis of hydrogen bond acceptor functional molecules: 0.5g of trimesic acid (2.4 mmol) and 0.78g (7.2 mmol) of 3-aminomethylpyridine are uniformly dispersed in 30mL of N, N-dimethylformamide, 0.93g of N, N-diisopropylethylamine (7.2 mmol) is added, stirring is carried out for 10 minutes, 2.73g of benzotriazol tetramethylurea hexafluorophosphate (7.2 mmol) is added, stirring is continued for 6 hours, the reaction is stopped, the N, N-dimethylformamide is removed by rotary evaporation, purification is carried out by column chromatography, and elution is carried out by a mixed solvent of dichloromethane and methanol with a volume ratio of 10:1, thereby obtaining 1.1g of hydrogen bond acceptor functional molecules.
Taking the prepared photocatalytic functional monomer and hydrogen bond acceptor functional molecule, respectively and uniformly dispersing in acetone in an ultrasonic manner, and preparing a mixed solution according to a molar ratio of 1:1 to obtain 1:1 an assembled porous photocatalyst.
Example 2
The preparation method of the photocatalytic functional monomer and the hydrogen bond acceptor functional molecule is the same as that of the example 1, the prepared photocatalytic functional monomer and the prepared hydrogen bond acceptor functional molecule are respectively and ultrasonically dispersed in acetone uniformly, and the molar ratio is 1:5 preparing a mixed solution to obtain 1:5 an assembled porous photocatalyst.
Example 3
The preparation method of the photocatalytic functional monomer and the hydrogen bond acceptor functional molecule is the same as that of the example 1, the prepared photocatalytic functional monomer and the prepared hydrogen bond acceptor functional molecule are respectively and ultrasonically dispersed in acetone uniformly, and the molar ratio is 1:2 preparing a mixed solution to obtain 1:2 an assembled porous photocatalyst.
Example 4
The preparation method of the photocatalytic functional monomer and the hydrogen bond acceptor functional molecule is the same as that of the example 1, the prepared photocatalytic functional monomer and the prepared hydrogen bond acceptor functional molecule are respectively and ultrasonically dispersed in acetone uniformly, and the molar ratio is 1:3 preparing a mixed solution to obtain 1:3 an assembled porous photocatalyst.
Example 5
The preparation method of the photocatalytic functional monomer and the hydrogen bond acceptor functional molecule is the same as that of the example 1, the prepared photocatalytic functional monomer and the prepared hydrogen bond acceptor functional molecule are respectively and ultrasonically dispersed in acetone uniformly, and the molar ratio is 1:4 preparing a mixed solution, namely obtaining 1:4 an assembled porous photocatalyst.
Application example 1
The nuclear magnetic resonance hydrogen spectrum, the carbon spectrum and the time-of-flight mass spectrum of the prepared photocatalytic monomer are shown in figure 1, and 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。
nuclear magnetic resonance hydrogen spectrum, carbon spectrum and flying of prepared hydrogen bond receptor functional moleculeThe specific data of the time mass spectrum 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。
characterization of the prepared supermolecule assembled porous photocatalyst by X-ray diffraction, fig. 2 is a schematic structural diagram of the photocatalytic monomer, the porous photocatalysts of example 1 and example 2, fig. 3 is a nitrogen adsorption-desorption curve of the porous photocatalysts of example 1 and example 2, and fig. 4 is an X-ray diffraction pattern of the photocatalytic monomer, the porous photocatalysts of example 1 and example 2. As can be seen in connection with fig. 2, 3 and 4, 1 of embodiment 1:1 shows a layer-by-layer assembled structure with a specific surface area of 18.3m 2 And/g, alternately stacking the photocatalytic monomer and the layered assembly of functional molecules to form a pore channel between the layers. 1 of example 2: the 5-assembled porous photocatalyst shows a hexagonal ordered structure with a specific surface area of 31.3m 2 And/g, honeycomb-shaped pore channels are formed in the structure. The pore channel structure formed in the porous catalyst can prevent agglomeration among photocatalytic monomers, is beneficial to rapid transfer of photoactive substances and improves photocatalytic efficiency.
The photocatalytic monomer, the porous photocatalysts of examples 1 and 2, were subjected to ultraviolet-visible spectrum and fluorescence spectrum tests by an ultraviolet-visible spectrometer and a fluorescence spectrometer, and as a result, as shown in fig. 5, the photocatalytic monomer exhibited a quenched fluorescence state in an acetone solution, and the light responsiveness was poor; 1 of example 1:1 the assembled porous photocatalyst presents a J-shaped aggregate state, and the light responsiveness is greatly improved; example 2 preparation 1: the 5-assembled porous photocatalyst spectrum exhibits a molecular state with the best photo-responsiveness.
The photocatalytic monomer, the porous photocatalysts of example 1 and example 2 were subjected to an active oxygen generation rate test, the molar concentration of the catalyst was 0.1mM, the concentration of the singlet oxygen probe was 0.1mM, and 520nm monochromatic light was used as an excitation light source, and the active oxygen generation rate results are shown in FIG. 6, 60s were consumed by the photocatalytic monomer for all singlet oxygen probes, and 1:1 the assembled porous photocatalyst was used for 24s only, whereas example 2, 1:5 the assembled photocatalyst is accelerated to 18s, which shows that the porous structure of the porous photocatalyst based on supermolecule recognition and assembly can effectively enhance the generation rate of active oxygen.
And comparing the degradation singlet oxygen probe rate after continuous illumination with an initial value to determine the structural stability of the assembled photocatalyst. As a result, as shown in fig. 7, the catalytic efficiency of the photocatalytic monomer was only 38% of the initial state after 4 hours of illumination, whereas the catalytic efficiencies of the porous photocatalysts of example 1 and example 2 were 75% and 91%, respectively, indicating that the porous photocatalysts of the present invention have excellent illumination stability.
Application example 2
The photocatalytic monomer, the porous photocatalysts of example 1 and example 2 were used for catalytic oxidation reaction of benzaldehyde, the molar concentration of the catalyst was 0.1mM, the concentration of benzaldehyde was 0.1M, the catalytic conversion rate was measured under AM1.5G simulated solar light, the test results are shown in FIG. 8, after 4 hours of catalytic reaction, the photocatalytic monomer was converted to only 50% of the catalytic substrate, while the conversion rate of both the porous photocatalysts of example 1 and example 2 was over 90%, and extremely high catalytic activity was exhibited. And, during the first 1 hour catalytic reaction, 1 of example 1:1 the conversion of the assembled porous photocatalyst was 28%, example 2, 1: the catalytic conversion rate of the porous photocatalyst assembled by 5 is 52%, which shows that the honeycomb porous structure has stronger catalytic conversion frequency.
The photocatalytic monomer, the porous photocatalyst of example 1 and example 2 was used for degradation of methyl orange, the concentration of methyl orange was 50mg/L, the concentration of catalyst was 0.1mM, and photodegradation rate measurement was performed under AM1.5G simulated solar light. The test results are shown in fig. 9, and 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 exhibit extremely strong photocatalytic degradation activity. Experimental results show that the porous photocatalyst based on molecular recognition and assembly provided by the invention has super-strong photocatalytic activity in the applications of photocatalytic conversion, pollutant degradation and the like, and has wide application prospects in the field of photocatalysis.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A porous photocatalyst, 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 acceptor functional molecule is shown as a formula (2);
the mole ratio of the photocatalytic monomer to the hydrogen bond acceptor functional molecule is 1:1 or 1:5, a step of;
the preparation method of the porous photocatalyst comprises the following steps: and respectively dissolving the photocatalytic monomer and the functional molecule in acetone, mixing the two, and performing rotary evaporation to obtain the porous photocatalyst.
2. The method for preparing the porous photocatalyst according to claim 1, comprising the steps of:
s1, stirring substrates dithienyl-pyrrolopyrrole dione, bromoisooctane and potassium tert-butoxide in a solvent a, performing rotary evaporation and purification to obtain an intermediate A; stirring the obtained intermediate A, boc-bromoethylamine and potassium tert-butoxide in a solvent a, steaming in a rotary way, and purifying to obtain an intermediate B; stirring the obtained intermediate B and trifluoroacetic acid in an ice water bath in a solvent B, steaming in a rotary way, and purifying to obtain a photocatalysis element;
s2, stirring trimesic acid, 2-aminomethylpyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation, and purifying 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 purification to obtain a photocatalytic monomer;
s3, stirring trimesic acid, 2-aminomethylpyridine, N-diisopropylethylamine and benzotriazole tetramethylurea hexafluorophosphate in a solvent a, performing rotary evaporation and purification to obtain a hydrogen bond acceptor functional molecule;
s4, respectively dissolving the obtained photocatalytic monomer and functional molecule in acetone, and then mixing the photocatalytic monomer and the functional molecule, and performing rotary evaporation to obtain the photocatalyst.
3. The method for preparing a porous photocatalyst according to claim 2, wherein in the step S1, the solvent a is N, N-dimethylformamide; the solvent b is dichloromethane; the stirring time is 3-7 h.
4. The method for preparing a porous photocatalyst according to claim 2, wherein in the step S1, the molar ratio of the substrate to bromoisooctane is 1 (1-2); the mol ratio of the intermediate A to Boc-bromoethylamine is 1 (1-2).
5. The method for preparing a porous photocatalyst according to claim 2, wherein in the step S2, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (2-3), the molar ratio of the intermediate C to the photocatalytic element is 1 (1-2), and the stirring time is 5h to 7h.
6. The method for preparing a porous photocatalyst according to claim 2, wherein in the step S3, the molar ratio of trimesic acid to 2-aminomethylpyridine is 1 (3-4); the stirring time is 5-7 h.
7. The method for preparing a porous photocatalyst according to claim 2, wherein in the 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.
8. The method for preparing a porous photocatalyst according to claim 2, wherein 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.
9. Use of the porous photocatalyst of claim 1, the porous photocatalyst prepared by the preparation method of any one of claims 2-8 in photocatalysis.
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