CN114479171B - Porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof - Google Patents
Porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof Download PDFInfo
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
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- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
The invention relates to a porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof. The porphyrin-based conjugated microporous polymer photothermal conversion sponge comprises: porphyrin-based conjugated microporous polymers, glucose-chitosan, and polyurethane sponges. The preparation method comprises the following steps: tetrabromophenyl porphyrin and p-phenylenediamine are subjected to Buchwald-Hartwig cross coupling reaction under the conditions of alkali, catalyst and ligand, the obtained porphyrin-based conjugated microporous polymer is mixed with a glucose-chitosan aqueous solution, polyurethane sponge is soaked in the obtained mixed solution, and heating and crosslinking are carried out. The preparation method has the advantages of simple operation and easily obtained materials; the porphyrin-based conjugated microporous polymer photothermal conversion sponge has the advantages of high photothermal conversion efficiency, high evaporation rate, recyclability, repeated utilization, good stability and the like.
Description
Technical Field
The invention belongs to the field of photothermal conversion materials and preparation and application thereof, and particularly relates to porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof.
Background
The photothermal conversion technology utilizes clean renewable sunlight irradiation objects to absorb sunlight and convert light energy into heat through mechanisms such as plasma resonance effect, conjugate effect, non-radiative relaxation, molecular thermal vibration and the like, so that seawater evaporation is accelerated and seawater desalination is realized. The conjugated microporous polymer is a conjugated organic porous material which is connected through covalent bonds and has a stable three-dimensional network structure. Based on abundant monomers and various synthesis methods, the molecular design of the conjugated microporous polymer is flexible, so that the surface properties of the polymer, such as important photothermal conversion parameters of a pore structure, a specific surface area, light absorption capacity, hydrophilicity and the like of the material can be regulated and controlled, and the conjugated microporous polymer is a photothermal conversion material with great research value.
Porphyrins are macromolecular heterocyclic compounds formed by four pyrrole rings interconnected by methine groups. The large ring has 18 highly conjugated electrons, and the whole ring presents a plane structure, which is beneficial to pi-electron delocalization. The compound derived from porphyrin has a permanent microporous structure and an expanded pi-conjugated skeleton, so that the compound constructed by taking porphyrin as a monomer has strong light absorption in a visible light-near infrared light region, and the polymer has good chemical stability. However, at present, most of the conjugated microporous polymers are in powder form, and are difficult to reprocess due to the characteristic of non-melting and non-dissolving after polymerization, and great limitations and challenges are brought to the application of the conjugated microporous polymers in seawater desalination, interface evaporation and the like.
Polydopamine-polyurethane sponge (appl. Energy,2017,206,63-69), a photothermal conversion sponge was made by in situ polymerization of dopamine on a polyurethane sponge skeleton. At 1kW m -2 The evaporation rate under illumination is 0.83kg m -2 h -1 Photo-thermalThe conversion efficiency was 52.2%. The black phosphorus-polyurethane sponge (Sol. RRL 2020,4,1900537) is prepared by a layer-by-layer assembly mode. At 1kW m -2 The evaporation rate under illumination is 1.082kg m -2 h -1 The photothermal conversion efficiency was 76.4%.
Disclosure of Invention
The invention aims to solve the technical problem of providing a porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof, filling the blank of the existing porphyrin-based conjugated microporous polymer for seawater desalination and photothermal conversion sponge thereof, and overcoming the defect of poor processability of a powdery polymer.
The invention provides a porphyrin-based conjugated microporous polymer photothermal conversion sponge, which comprises: porphyrin-based conjugated microporous polymers, glucose-chitosan, and polyurethane sponges; the structural formula of the porphyrin-based conjugated microporous polymer is as follows:
preferably, the porphyrin-based conjugated microporous polymer photothermal conversion sponge is obtained by heating and crosslinking porphyrin-based conjugated microporous polymer, glucose-chitosan and polyurethane sponge on polyurethane sponge.
Preferably, the mass ratio of the porphyrin-based conjugated microporous polymer to the glucose-chitosan is 1-9:2-3.
The invention also provides a preparation method of the porphyrin-based conjugated microporous polymer photothermal conversion sponge, which comprises the following steps:
(1) Tetrabromophenyl porphyrin and p-phenylenediamine are mixed, alkali, catalyst and ligand are added, solvent is added in nitrogen atmosphere, buchwald-Hartwig cross coupling reaction is carried out, washing, filtering and drying are carried out, and porphyrin-based conjugated microporous polymer is obtained;
(2) And mixing the porphyrin-based conjugated microporous polymer with a glucose-chitosan aqueous solution, soaking polyurethane sponge in the obtained mixed solution, and heating for crosslinking to obtain the porphyrin-based conjugated microporous polymer photothermal conversion sponge.
Preferably, the molar ratio of tetrabromophytorphyrin to p-phenylenediamine, base, catalyst and ligand in step (1) is 0.2-0.6.
Preferably, the ratio of the tetrabromophytin porphyrin to the solvent in the step (1) is 0.2mmol.
Preferably, the base in step (1) is sodium tert-butoxide; the catalyst is bis (dibenzylideneacetone) palladium.
Preferably, the ligand in the step (1) is 2-dicyclohexyl phosphorus-2,4,6-triisopropyl biphenyl; the solvent is anhydrous toluene.
Preferably, the Buchwald-Hartwig cross-coupling reaction temperature in the step (1) is 100-120 ℃, and the reaction time is 40-55h.
Preferably, the nitrogen atmosphere in step (1) is: a50 mL Schlenk tube was degassed under a double-row tube by introducing nitrogen for 3 times, each time for 5min, and after introducing nitrogen for 1min, anhydrous toluene was added under the condition of introducing nitrogen.
Preferably, the washing in step (1) is: the polymer was washed with 200mL each of chloroform, methanol and water sequentially at 55 ℃ with stirring for 12h each time.
Preferably, the filtration in the step (1) is suction filtration, and chloroform, methanol or water is used for washing during the suction filtration.
Preferably, the drying in step (1) is: drying in a vacuum oven at 100 ℃ for 48h.
Preferably, the method for preparing the glucose-chitosan aqueous solution in the step (2) comprises the following steps: dissolving D-glucose salt in water, adding cation exchange resin, and mixing the obtained glucose salt-cation exchange resin mixed solution with chitosan according to the proportion of 100-140mL: mixing 8-10g, adding deionized water, stirring for 20-26h, filtering, carrying out rotary evaporation on the filtrate, adding methanol, filtering, carrying out vacuum drying on the obtained solid, and dispersing in deionized water to obtain the D-glucose-cation exchange resin composite material, wherein the ratio of D-glucose salt to cation exchange resin is 7g:30mL.
Preferably, the mass ratio of the porphyrin-based conjugated microporous polymer to the glucose-chitosan aqueous solution in the step (2) is 20-180mg.
Preferably, the concentration of the glucose-chitosan aqueous solution in the step (2) is 0.2-0.3wt%.
Preferably, the polyurethane sponge in the step (2) is in the shape of a cylinder with a diameter of 4.5cm and a height of 1 cm.
Preferably, the thermal crosslinking in step (2) is: squeezing the soaked polyurethane sponge to obtain excessive liquid, drying at 80 deg.C for 1h, and reacting at 150-170 deg.C for 8-15min.
Preferably, the soaking and the heat crosslinking in the step (2) are repeated for a plurality of times until the mixed solution is completely absorbed by the polyurethane sea.
The invention also provides application of the porphyrin-based conjugated microporous polymer photothermal conversion sponge in seawater desalination or wastewater purification, for example, the porphyrin-based conjugated microporous polymer photothermal conversion sponge is used as a light absorption and pyrogenic desalination material for seawater or sewage and wastewater.
The porphyrin-based conjugated microporous polymer modified sponge is put into seawater or dye wastewater, and water evaporation is carried out under the irradiation of light. Wherein the incident light is simulated sunlight and natural sunlight, and the light intensity of the simulated sunlight is 1kW m -2 h -1 The seawater is yellow sea water, and the dye wastewater is methylene blue aqueous solution with the concentration of 100ppm.
The invention adopts Buchwald-Hartwig cross coupling reaction to prepare the conjugated microporous polymer and uses the conjugated microporous polymer as a photothermal conversion material, and the porphyrin-based conjugated microporous polymer modified sponge is obtained by loading the polymer on the surface of a sponge framework through a simple dip-coating method. The method is simple and effective, not only stably loads the polymer sponge through the cross-linked glucose-chitosan, solves the problem that polymer powder is difficult to recover and process, but also provides a mass transfer channel and a heat preservation environment for photo-thermal evaporation of seawater. Due to the low thermal conductivity and the multi-pore channel structure of the polyurethane sponge, the dual functions of heat preservation, water absorption and mass transfer are achieved; the polymer powder is used as a light absorbent on a polyurethane sponge framework, seawater in pore channels inside the sponge is heated through photo-thermal conversion, and heat is preserved through the polyurethane sponge to avoid heat loss; finally, the polymer sponge realizes high-efficiency seawater evaporation and high photothermal conversion efficiency. At 1kW m -2 Under illumination, the sponge photo-thermal conversion efficiency modified by the porphyrin-based conjugated microporous polymer reaches 81.6 percent, and the evaporation rate is 1.31kg m -2 h -1 ) And the purification efficiency of the dye wastewater reaches 99.2 percent. The sponge loaded with the polymer remarkably improves the evaporation rate of seawater, the highest evaporation rate reaches 3 times of that of pure polyurethane sponge, and the photothermal conversion efficiency is 2.63 times of that of the pure polyurethane sponge.
Advantageous effects
The invention has the advantages of simple operation, easily obtained materials, high photo-thermal conversion efficiency, high evaporation rate, recycling for multiple times, good stability and the like. The sponge size can be adjusted according to the actual scale, and the method has good application prospect in the field of efficient and energy-saving desalination and purification of seawater and sewage.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of the polymer obtained in example 1;
FIG. 2 is a powder X-ray diffraction pattern of the polymer obtained in example 1;
FIG. 3 is a thermogravimetric analysis of the polymer obtained in example 1;
FIG. 4 shows N of the polymer obtained in example 1 2 An adsorption-desorption curve;
FIG. 5 is a graph of the theoretical pore size distribution of porphyrin-based conjugated microporous polymer as a function of delocalized density in example 1;
FIG. 6 is a scanning electron micrograph of a polymer sponge according to example 2;
FIG. 7 is a graph of temperature versus time for simulated solar illumination for different polymer loadings of the photothermal conversion sponge of example 3;
FIG. 8 is a graph of evaporation rate versus light-to-heat conversion efficiency for the polymer-modified sponge of example 3 under simulated solar illumination;
FIG. 9 is a plot of the evaporation rate of the polymer-modified sponge of example 4 under natural sunlight;
FIG. 10 is a UV-Vis absorbance curve of the dye waste water and its evaporated water before purification of the polymer modified sponge in example 5;
FIG. 11 is a graph of 5 cycle evaporation rate and light-to-heat conversion efficiency for the polymer-modified sponge of example 6.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Examples source of raw materials: tetra (4-bromophenyl) porphyrin (meso-Tetra (p-bromophenyl) porphyrin, TP, 97%) was purchased from shanghaienqian biotechnology limited, p-Phenylenediamine (p-Phenylenediamine, 99%), toluene (Toluene, 99%), sodium tert-butoxide (Sodium tert-butoxide, naOtBu, 99%), 2-dicyclohexylphosphorus-2,4,6-triisopropylbiphenyl (2-Dicyclohexylphosphino-2 ',4',6' -tripropybiphenyl, XPhos, 98%) was purchased from shanghai pharmaceutical company chemical company limited, bis (dibenzylideneacetone) palladium (0) (Pd (dba) 2,99%) was purchased from michelin reagent company, D-glucose potassium salt (D-glucose acid salt, sa, 98%) was purchased from Sigma-Aldrich, sigma-Aldrich resin, sigma-Aldrich. Polyurethane sponge (PU) is a commercial sponge.
Example 1
Preparation of porphyrin-based conjugated microporous polymer as photothermal conversion material.
The preparation method comprises the following steps: placing tetrabromophenylporphyrin (186mg, 0.2mmol) and p-phenylenediamine (64.8mg, 0.6mmol) into a 50mL reaction tube at normal temperature and pressure, adding sodium tert-butoxide (100mg, 1.04mmol), 2-dicyclohexylphosphorus-2,4,6-triisopropylbiphenyl (11.44mg, 0.024mmol) and bis (dibenzylideneacetone) palladium (9.2mg, 0.016mmol), adding 20mL anhydrous toluene under nitrogen atmosphere, reacting for 48h at 110 ℃, washing and filtering the prepared polymer with chloroform, methanol and water, and drying for 48h in a 100 ℃ vacuum oven to obtain the porphyrin-based conjugated microporous polymer, namely PACMP-2.
The amount of p-phenylenediamine added in the above preparation process was changed to 21.6mg (0.2 mmol), and the rest was the same as in the above process, to obtain a porphyrin-based conjugated microporous polymer, which was designated as PACMP-1.
The Fourier transform infrared spectrum of the polymer obtained in this example is shown in FIG. 1, in which 1300cm -1 And 3384cm -1 C-N and N-H bonds of secondary amines appeared nearby and were located at 1068cm -1 The C-Br bond disappears, and the synthesis of the conjugated polymer structure is proved.
The powder X-ray diffraction pattern of the polymer obtained in this example is shown in FIG. 2, and no significant peak appears in the polymer after the coupling reaction, indicating that the polymer sample is an amorphous organic polymer.
The thermogravimetric analysis chart of the polymer obtained in this example is shown in FIG. 3, in which the initial decomposition temperature of the polymer is about 400-450 deg.C, the residue mass after heating to 900 deg.C is about 64%, the PACMP-1 coke yield is 62.7%, the PACMP-2 coke yield is 61.5%, and the thermal stability is good.
N of the Polymer obtained in this example 2 The absorption-desorption curve is shown in FIG. 4, and the specific surface area of PACMP-1 is calculated by using Brunauer-Emmett-Teller (BET) model and is 96m 2 g -1 The specific surface area of PACMP-2 is 221m 2 (ii) in terms of/g. The theoretical pore size distribution of the delocalized density function is shown in fig. 5, and the porphyrin-based conjugated microporous polymer has a hierarchical pore (microporous, mesoporous) distribution. The post-desorption curve is not completely closed with the adsorption curve due to the partial N 2 Remaining in the pores of the sample polymer and not being completely desorbed.
Example 2
Preparation OF porphyrin-BASED conjugated microporous POLYMER modified sponge for seawater desalination and dye wastewater purification comprises preparation OF glucose-chitosan solution (preparation method reference: vogt, B.D.; cavicchi, K.A.; ye, C.; seo, J.; SOLID STATE CONVERSION OF BIO-BASED ORGANIC SALTS TO GENERATE POLYMER COATINGS.), and POLYMER modified sponge.
The preparation method comprises the following steps: fully dissolving 7g D-glucose potassium salt in 100mL deionized water, adding 30mL cation exchange resin, and stirring for 15min until no particles exist, thereby obtaining a glucose potassium salt-ion exchange resin mixed filtrate. Mixing the mixed filtrate with 9.1g of chitosan, adding deionized water and stirring for 24 hours to form a uniform glucose-chitosan organic salt solution. The solution was purified by filtration and the collected filtrate was rotary evaporated at 40 ℃ to obtain glucose-chitosan adhesive. Before use, 300mL of methanol was added to the adhesive and the filtered solid was dried in an oven at 50 ℃ for 12h under vacuum. Finally, 2.5g of the full solution of adhesive powder was placed in 97.5mL of deionized water to make a 2.5wt% glucose-chitosan solution.
0,20,60,120,180mg of porphyrin-based conjugated microporous polymer powder (PACMP-2) obtained in example 1 was dispersed in 20mL of glucose-chitosan solution, and the mixture was subjected to ultrasonic treatment for 30min to obtain a polymer adhesive mixture. Soaking the mixture in a cake-shaped polyurethane sponge with diameter of 45mm and height of 10mm, squeezing the excess liquid, drying at 80 deg.C for 1h, and transferring to a 160 deg.C oven for reaction for 10min. Repeating the above operations for many times until the mixed solution is completely absorbed by the Sponge and dried to obtain polymer modified Sponge (PU Sponge, PACS-20, PACS-60, PACS-120 and PACS-180).
The scanning electron microscope image of the polymer modified sponge obtained in this example is shown in fig. 6, and the polymer powder is uniformly loaded on the surface of the sponge skeleton to form the polymer outer layer.
Example 3
The application of the porphyrin-based conjugated microporous polymer modified sponge in seawater desalination is as follows:
100mL of yellow sea water is added into a small beaker with the diameter of 4.5cm, the polymer sponge in the example 2 is placed on the surface of the sea water, and the total mass of the beaker, the sea water and the sponge is weighed and recorded; vertically irradiating for 1h under standard simulated sunlight, and recording real-time temperature and infrared thermal image pictures by using an infrared thermal imager. After the end of weighing the total mass of the beaker, the seawater and the sponge, the results are shown in fig. 7 and 8, fig. 7 illustrates that the temperature of the sponge loaded with the polymer is remarkably increased under the illumination, and the surface temperature of the polymer sponge is obviously higher than that of the pure polyurethane sponge under the same conditions; fig. 8 shows the evaporation rate and the light-to-heat conversion efficiency of polymer sponges and pure polyurethane sponges on seawater under illumination, illustrating that the evaporation rate and the light-to-heat conversion efficiency of polymer sponges gradually increase by loading reasonable mass of polymer, and are much higher than pure polyurethane sponges.
Example 4
The evaporation application of porphyrin-based conjugated microporous polymer modified sponge PACS-120 under natural sunlight illumination comprises the following specific steps:
100mL of yellow sea water is added into a small beaker with the diameter of 4.5cm, the polymer sponge PACS-120 in example 2 is placed on the surface of the sea water, and the total mass of the beaker, the sea water and the sponge is weighed and recorded; the total mass of the beaker, the seawater and the sponge is weighed at intervals of 1h under natural sunlight from 9 am to 19 pm. The control experiment was conducted with pure yellow sea water under the same conditions and weighed at 1h intervals. The results are shown in FIG. 9, which shows that under natural illumination, the polymer sponge PACS-120 accelerates the evaporation of seawater, the evaporation rate is obviously higher than that of pure seawater, and the highest evaporation rate is 2.4kg m -2 h -1 And is 1.9 times of the evaporation rate of the seawater under the same conditions.
Example 5
The sponge PACS-120 modified by porphyrin-based conjugated microporous polymer is applied to dye wastewater purification under simulated solar illumination, and the specific method comprises the following steps:
100mL of methylene blue solution with the concentration of 100ppm is added into a small beaker with the diameter of 4.5cm, the polymer sponge PACS-120 in example 2 is placed on the surface of the dye solution, and the total mass of the beaker, the solution and the sponge is weighed and recorded; irradiating for 1h under simulated sunlight, and weighing the total mass of the beaker, the solution and the sponge after the irradiation is finished. FIG. 10 shows that the polymer sponge PACS-120 has high purification efficiency of dye water through evaporation, and can remove 99.2% of dye.
Example 6
The evaporation performance stability test of the porphyrin-based conjugated microporous polymer modified sponge PACS-120 under simulated solar illumination comprises the following specific steps:
100mL of yellow sea water is added into a small beaker with the diameter of 4.5cm, the polymer sponge PACS-120 in example 2 is placed on the surface of the sea water, and the total mass of the beaker, the solution and the sponge is weighed and recorded; irradiating for 1h under simulated sunlight, and weighing the total mass of the beaker, the solution and the sponge after the irradiation is finished. Repeating the above operation for 5 times, calculating evaporation rate and photothermal conversionEfficiency. FIG. 11 shows that: the polymer sponge PACS-120 passes 5 times of cyclic evaporation tests, and the evaporation rate and the photothermal conversion efficiency of the polymer sponge PACS-120 are respectively kept at 1.3kg m -2 h -1 And 80%, indicating that the polymer sponge has good cycling stability.
At present, the photo-thermal conversion material is prepared from metal powder materials, semiconductor powder materials and the like commonly used for seawater desalination, and the evaporation rate of the photo-thermal conversion material is 1-2 kg m -2 h -1 However, the metal-based material has a risk of high cost, metal leakage, and the like, and the semiconductor material has a limited light absorption capability, and the like. The preparation method has the advantages of simple operation, wide application, high efficiency, difficult falling of powder, easy recovery of sponge and evaporation rate of 2.4kg m -2 h -1 Compared with the prior art, the evaporation rate is stable and efficient, and the problem that the powder material is difficult to process because the powder material is not melted and dissolved is effectively solved.
Claims (9)
1. A porphyrin-based conjugated microporous polymer photothermal conversion sponge, comprising: porphyrin-based conjugated microporous polymers, glucose-chitosan, and polyurethane sponges; the structural formula of the porphyrin-based conjugated microporous polymer is as follows:
2. the porphyrin-based conjugated microporous polymer photothermal conversion sponge according to claim 1, wherein the porphyrin-based conjugated microporous polymer photothermal conversion sponge is obtained by heat crosslinking of a porphyrin-based conjugated microporous polymer, glucose-chitosan and a polyurethane sponge on a polyurethane sponge.
3. The porphyrin-based conjugated microporous polymer photothermal conversion sponge according to claim 1, wherein the mass ratio of the porphyrin-based conjugated microporous polymer to the glucose-chitosan is 1-9:2-3.
4. A method for preparing porphyrin-based conjugated microporous polymer photothermal conversion sponge comprises the following steps:
(1) Tetrabromophenyl porphyrin and p-phenylenediamine are mixed, alkali, catalyst and ligand are added, solvent is added under the atmosphere of nitrogen, buchwald-Hartwig cross coupling reaction is carried out, washing, filtering and drying are carried out, thus obtaining porphyrin-based conjugated microporous polymer;
(2) And mixing the porphyrin-based conjugated microporous polymer with a glucose-chitosan aqueous solution, soaking polyurethane sponge in the obtained mixed solution, and heating for crosslinking to obtain the porphyrin-based conjugated microporous polymer photothermal conversion sponge.
5. The preparation method according to claim 4, wherein the molar ratio of tetrabromophytin to p-phenylenediamine, base, catalyst and ligand in step (1) is 0.2 to 0.2.6; the ratio of the tetrabromophenylporphyrin to the solvent is 0.2mmol.
6. The method according to claim 4, wherein the base in the step (1) is sodium tert-butoxide; the catalyst is bis (dibenzylidene acetone) palladium; the ligand is 2-dicyclohexyl phosphorus-2,4,6-triisopropyl biphenyl; the solvent is anhydrous toluene.
7. The preparation method according to claim 4, wherein the Buchwald-Hartwig cross-coupling reaction temperature in the step (1) is 100-120 ℃, and the reaction time is 40-55h.
8. The preparation method according to claim 4, wherein the mass ratio of the porphyrin-based conjugated microporous polymer to the glucose-chitosan aqueous solution in step (2) is 20-180mg; the concentration of the glucose-chitosan aqueous solution is 0.2-0.3wt%; the heating crosslinking is as follows: squeezing the soaked polyurethane sponge to obtain excessive liquid, drying, and reacting at 150-170 deg.C for 8-15min.
9. Use of the porphyrin-based conjugated microporous polymer photothermal conversion sponge according to claim 1 for desalination of sea water or purification of wastewater.
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