Preparation of organic photothermal materials based on phenazine and anthraquinone derivative acceptors and their application in hydropower cogeneration

Abstract

The present invention discloses a method for preparing an organic photothermal material based on a phenazine and anthraquinone derivative acceptor and its application in the field of water and power cogeneration. The present invention combines two strong electron-withdrawing groups into one molecule, and constructs an organic photothermal material DDPA-PDN using a rigid planar acceptor PDN with strong electron-withdrawing ability. The new compound has strong intramolecular charge transfer characteristics and a conjugated rigid planar skeleton, has a wide spectrum absorption of 300-850nm in the solid state, and has excellent photothermal effect and light / thermal stability. Under 655nm laser irradiation, the solid photothermal conversion efficiency of the DDPA-PDN molecule can reach 56.23%. In addition, the DDPA-PDN cellulose paper with rich water flow microchannels is integrated with a thermoelectric device, so that it achieves an evaporation efficiency of up to 61.06% under one sunlight intensity, while generating an open circuit voltage of 43mV. The present invention demonstrates the ability of organic photothermal materials in collecting and utilizing solar energy, thereby providing useful value for it in the field of water and power cogeneration.

Description

Technical Field

[0001] The present invention belongs to the technical energy field of water and power cogeneration, and specifically relates to a method for preparing an organic photothermal material based on a phenazine and anthraquinone derivative acceptor and its application in the field of water and power cogeneration. Background Art

[0002] With the rapid growth of population and the continuous improvement of living standards, the consumption of fossil fuels is becoming more and more serious, making the water purification system that relies on fossil fuels unsustainable. Therefore, it is necessary to develop an eco-friendly technology to achieve the goal of sustainable development. As an alternative to fossil fuels, solar energy is a renewable, green and pollution-free energy source, so it can be used to evaporate water and generate electricity without consuming fossil fuels. In the process of solar thermal conversion, the evaporation mode of water has a crucial influence on the photothermal conversion efficiency and evaporation rate. At present, the selective heating system in the form of interfacial evaporation challenges the feasibility of thermoelectric conversion to solve the energy crisis. Therefore, it is urgent to develop an efficient photothermal material to construct a solar-driven water-electricity integrated device.

[0003] At present, the commonly used photothermal materials mainly include carbon-based inorganic materials, metal-based inorganic materials, organic polymers, organic small molecule materials, etc. Among them, organic small molecule photothermal materials have attracted more and more attention due to their unique advantages such as processability, structural diversity and adjustability. As solar energy absorption materials, organic small molecule photothermal materials can collect waste heat to generate electricity during water evaporation and have broad application prospects. Although organic photothermal small molecules have broad application prospects in solar energy acquisition and conversion, further exploration is needed to broaden their absorption spectra and promote their photothermal conversion so that they can be used in high-performance water evaporation / thermoelectric devices. In general, organic conjugated molecules with donor-acceptor (DA) structures can cause a large red shift in the absorption spectrum through effective electron delocalization. In addition, the conjugated rigid planar structure helps to increase the π-π stacking of the aggregated state, thereby further broadening the absorption spectrum. More interestingly, according to the energy gap law, the resulting small energy gap may promote the generation of heat by non-radiative decay. Therefore, the development of organic small molecule materials with DA structure and conjugated rigid planar skeleton is crucial for high-performance evaporation / thermoelectric devices. Summary of the invention

[0004] The purpose of the present invention is to solve the current problems of shortage of fresh water resources and low utilization rate of new renewable energy. To this end, a method for preparing an organic photothermal material based on a phenazine and anthraquinone derivative acceptor and its application in the field of water and power cogeneration are provided.

[0005] To achieve the above purpose, the present invention adopts the following steps to prepare the organic photothermal material:

[0006] The present invention provides an organic photothermal material DDPA-PDN based on a phenazine and anthraquinone derivative acceptor, the structural formula of which is as follows (Formula 1):

[0007]

[0008] The synthetic route adopted in the present invention can be represented by the following reaction formula:

[0009]

[0010] The preparation of DDPA-PDN is shown in Formula 1:

[0011] Step 1, synthesis of compound DDPA-PD:

[0012] First, add 3,6-dibromophenanthrene-9,10-dione, diphenylamine, tri(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), cesium carbonate (Cs2CO3), and 1.0M tri-tert-butylphosphine (P(t-Bu)3) toluene solution in sequence into a three-necked flask containing toluene solution and stir to dissolve.

[0013] Secondly, the reaction mixture was reacted at a high temperature of 110° C. under a nitrogen atmosphere for 24 hours.

[0014] Finally, the mixture was cooled to room temperature and distilled water was added to quench the reaction.

[0015] After that, the mixture was extracted with dichloromethane, the combined organic layers were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure.

[0016] The obtained crude product was then separated and purified by column chromatography to obtain a dark red solid and compound DDPA-PD;

[0017] Step 2, synthesis of compound DDPA-PDN:

[0018] First, the dark red solid DDPA-PD and 5,6-diaminoanthraquinone synthesized in step 1 are poured into a dry three-necked flask, and then acetic acid is added to fully dissolve them.

[0019] Secondly, the reaction mixture was reacted at a high temperature of 120° C. under nitrogen conditions for 12 hours.

[0020] Finally, the mixture was cooled to room temperature and poured into water, and then filtered. The filter cake was then dissolved in dichloromethane, dried over anhydrous sodium sulfate, and then water was removed under reduced pressure to obtain a crude product.

[0021] The crude product was separated and purified by column chromatography to obtain dark red solid DDPA-PDN.

[0022] The beneficial effects of the present invention are:

[0023] (1) The organic photothermal material DDPA-PDN of the present invention has a small molecular structure, a simple synthesis route, a high yield (about 50%), and can be produced on a large scale commercially;

[0024] (2) The organic photothermal material DDPA-PDN of the present invention can act as a light absorbing material, which has a wide spectrum absorption of 350-850nm and a photothermal conversion efficiency of 56.23%, which lays a practical foundation for the application of solar-driven water and power cogeneration;

[0025] (3) The DDPA-PDN filter paper of the present invention can simultaneously produce water and electricity, and the solar water evaporation efficiency under one sunlight intensity reaches 61.06%, and an open circuit voltage of 43mV can be generated at the same time, indicating that the material can be well applied in the technical energy field of water and electricity cogeneration. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the synthesis route diagram of DDPA-PDN;

[0027] Figure 2 is the laser stabilization diagram of DDPA-PDN;

[0028] Figure 3 It is the thermogravimetric analysis curve of DDPA-PDN;

[0029] Figure 4 is the scanning electron microscopy image of DDPA-PDN filter paper;

[0030] Figure 5 is the UV absorption graph of DDPA-PDN filter paper;

[0031] Figure 6 It is the temperature difference diagram of DDPA-PDN hydropower cogeneration;

[0032] Figure 7 The voltage diagram for DDPA-PDN hydropower cogeneration;

[0033] Figure 8 This is the rate diagram of DDPA-PDN hydropower cogeneration. DETAILED DESCRIPTION

[0034] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0035] Embodiment 1 of the present invention:

[0036] Synthesis of compound DDPA-PD: First, add 3,6-dibromophenanthrene-9,10-dione (3.66 g, 10 mmol), diphenylamine (4.22 g, 25 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (275 mg, 0.3 mmol), cesium carbonate (Cs2CO3) (13.04 g, 40 mmol), and 1.0 M tri-tert-butylphosphine (P(t-Bu)3) toluene solution (3 ml) in sequence into a three-necked flask containing a toluene solution (100 ml) and stir to dissolve.

[0037] Secondly, the reaction mixture was reacted at a high temperature of 110° C. under a nitrogen atmosphere for 24 hours.

[0038] Finally, the mixture was cooled to room temperature and distilled water was added to quench the reaction.

[0039] After that, the mixture was extracted with dichloromethane, the combined organic layers were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure.

[0040] The obtained crude product was then separated and purified by column chromatography using dichloromethane as an eluent to obtain a dark red solid and compound DDPA-PD;

[0041] Synthesis of compound DDPA-PDN: First, pour the dark red solid DDPA-PD (2.17 g, 4 mmol) and 5,6-diaminoanthraquinone (4.80 g, 20 mmol) synthesized in step 1 into a dry three-necked flask, and then add 30 ml of acetic acid to fully dissolve them.

[0042] Secondly, the reaction mixture was reacted at a high temperature of 120° C. under nitrogen conditions for 12 hours.

[0043] Finally, the mixture was cooled to room temperature and poured into water, and then filtered. The filter cake was then dissolved in dichloromethane, dried over anhydrous sodium sulfate, and then water was removed under reduced pressure to obtain a crude product.

[0044] The crude product was purified by column chromatography using dichloromethane as eluent to afford DDPA-PDN as a dark red solid.

[0045] The photostability of DDPA-PDN: The temperature change of 4mg solid powder of DDPA-PDN was tested under five consecutive cycles of on-off laser irradiation, using a 730nm laser with an energy density of 0.8W / cm 2 , the laser is switched on and off every 60 seconds, and the temperature is recorded every 2 seconds;

[0046] Thermal stability of DDPA-PDN: The mass change of DDPA-PDN solid powder was measured by heating from 25°C to 800°C at a rate of 10K / min in a nitrogen atmosphere using a TA Q500 thermogravimetric analyzer.

[0047] Photothermal conversion performance of DDPA-PDN: First, the UV absorption spectrum of DDPA-PDN solid powder was measured by UV spectrophotometer to obtain its absorbance at 655nm. Then, DDPA-PDN was evenly spin-coated on a quartz wafer to form a thin film, and the 0.8W / cm 2 The material was irradiated with a 655nm laser to the highest temperature, the laser was turned off and timing was started, the temperature was recorded every 5 seconds, the temperature drop of the DDPA-PDN film from 0 to 350 seconds was measured and a Tt cooling curve was prepared. Finally, the photothermal conversion efficiency of DDPA-PDN was calculated.

[0048] Embodiment 2 of the present invention:

[0049] Preparation of DDPA-PDN filter paper: First, 5 mg of DDPA-PDN was dissolved in a small amount of DCM solvent, and then the solution was dripped on the surface of the filter paper using a pipette, and the operation was repeated so that DDPA-PDN was successfully impregnated on the filter paper. Finally, the filter paper was dried in natural wind to obtain the photothermal absorption layer DDPA-PDN filter paper;

[0050] DDPA-PDN loading condition of filter paper: The morphology of blank filter paper and filter paper loaded with 5 mg DDPA-PDN was observed using a scanning electron microscope (EM-30plus);

[0051] Absorption properties of DDPA-PDN filter paper: The UV absorption of blank filter paper and DDPA-PDN filter paper was measured at 300-1000 nm using a Hitachi U-4100 UV / Vis / NIR spectrophotometer;

[0052] Temperature difference change of hydropower cogeneration: Use CEL-S500 / 350 xenon lamp light source with standard AM 1.5G spectrum filter to irradiate DDPA-PDN filter paper at 1, 2, and 5 sun light intensity, and use infrared thermal imager (TESTO-869) to record the change of filter paper surface temperature and water temperature. Record the filter paper surface temperature and water temperature every 30 seconds, and test the change of temperature difference within 5 minutes;

[0053] Application of water and power cogeneration: The water and power cogeneration experiment was conducted using a CBL-S500 / 350 xenon lamp light source with a standard AM 1.5G spectral filter. The DDPA-PDN filter paper was illuminated at 1 sun intensity, and the mass loss of water was monitored using an analytical balance while the open circuit voltage data was recorded by a Keithley 6514 system;

[0054] The above descriptions are only preferred embodiments of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing the compound DDPA-PDN, characterized in that: The following steps are involved: First, pour the dark red solid DDPA-PD and 5,6-diaminoanthraquinone into a dry three-necked flask, and then add acetic acid to fully dissolve them; Secondly, the reaction mixture was reacted at a high temperature of 120°C under nitrogen for 12 hours; Finally, the mixture was cooled to room temperature and poured into water, and then filtered. The filter cake was then dissolved in dichloromethane, dried over anhydrous sodium sulfate, and then water was removed under reduced pressure to obtain a crude product. The crude product was separated and purified by column chromatography to obtain dark red solid DDPA-PDN; The chemical structure of DDPA-PD is: The chemical structure of DDPA-PDN is:

2. The method for preparing the compound DDPA-PDN according to claim 1, characterized in that: The preparation process of the compound DDPA-PD is as follows: First, 3,6-dibromophenanthrene-9,10-dione, diphenylamine, tris(dibenzylideneacetone)dipalladium(0), cesium carbonate, and 1.0 M tri-tert-butylphosphine toluene solution were sequentially added into a three-necked flask containing a toluene solution and stirred to dissolve; Secondly, the reaction mixture was reacted at a high temperature of 110°C under a nitrogen atmosphere for 24 hours; Finally, the mixture was cooled to room temperature and distilled water was added to quench the reaction; The mixture was then extracted with dichloromethane, the combined organic layers were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure; The obtained crude product is then separated and purified by column chromatography to obtain a dark red solid and the compound DDPA-PD.

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