Preparation method of a photothermal conversion material based on supramolecular co-crystals

Abstract

The application relates to the technical field of photothermal materials, in particular to a preparation method of a photothermal conversion material based on a supramolecular co-crystal. The method comprises the following steps: step 1, activating a co-crystal material based on a hetero[4]arene; step 2, taking thiophene and the activated co-crystal material based on the hetero[4]arene, and preparing the photothermal conversion material by adsorbing the gas volatilized from the thiophene through the activated co-crystal material based on the hetero[4]arene. The preparation process adopts raw materials which are easy to obtain, reduces the preparation cost, simplifies the preparation steps, makes the synthesis of the photothermal conversion material more economical and efficient, helps to improve the preparation feasibility and scalability, and lays a foundation for large-scale production and commercial application.

Description

Technical Field

[0001] This invention relates to the field of photothermal materials technology, and more particularly to a method for preparing a photothermal conversion material based on supramolecular eutectic. Background Technology

[0002] Photothermal materials are a class of materials that can convert absorbed light energy into heat energy. With the development of optical technology, photothermal conversion materials are increasingly widely used in chemical, energy, sensing, and life sciences. Near-infrared (NIR) photothermal materials, which convert light energy into heat energy by absorbing near-infrared light, have always attracted much attention. Traditional organic NIR conversion materials not only require complex synthesis procedures but are also prone to photobleaching under light irradiation. These drawbacks lead to high costs in the photothermal conversion process and the risk of performance degradation. Traditional polymer photothermal nanomaterials have poor thermal and chemical stability and low photothermal conversion efficiency, failing to meet current needs. Therefore, there is an urgent need for an innovative photothermal conversion material to overcome these technical challenges, improve the thermal and chemical stability of photothermal materials, reduce operational complexity, lower production costs, and balance economic and environmental benefits to achieve sustainable material utilization.

[0003] Patent CN117224675A discloses a two-dimensional flower-shaped near-infrared responsive water-soluble photothermal conversion nanomaterial, its synthesis method, and near-infrared applications. This invention achieves uniform loading of gold nanoparticles and constructs a composite material of inorganic nanomaterials modified with biomolecules and biomimetic materials.

[0004] Patent CN117285379A discloses a photothermal conversion mineral material, its preparation method, and its applications. This mineral material can self-assemble into a unified system on a liquid surface through surface tension, thus exhibiting excellent photothermal conversion performance, water absorption performance, and thermal insulation performance. However, its preparation is complex and expensive.

[0005] Currently, some photothermal materials suffer from a series of technical drawbacks, including low photothermal conversion efficiency, stability issues, high manufacturing costs, lack of environmental friendliness, and limited controllability. These problems restrict the performance and sustainability of these materials in practical applications. Therefore, research on photothermal materials still needs further improvement and innovation to overcome these shortcomings and meet the requirements of different application scenarios for high efficiency, stability, environmental friendliness, and strong controllability. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a photothermal conversion material based on supramolecular eutectic, which aims to overcome the shortcomings of current photothermal materials such as low photothermal conversion efficiency, poor stability, and high preparation cost. This method achieves high efficiency in the photothermal conversion process while taking into account preparation cost and environmental friendliness, thereby promoting innovation in the field of photothermal materials and meeting the growing demand for clean energy and green technologies.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows:

[0008] This invention provides a method for preparing a photothermal conversion material based on supramolecular eutectic, the method comprising the following steps:

[0009] Step 1: Activate the eutectic material based on hetero[4]aromatics;

[0010] Step 2: Take thiophene and activated hetero[4]aromatic eutectic material, and use the activated hetero[4]aromatic eutectic material to adsorb the gas volatilized from thiophene to prepare the photothermal conversion material.

[0011] In the above technical solution, further, in step 1, the activation temperature is not lower than 120°C and the activation time is not less than 9 hours.

[0012] In the above technical solution, further, in step 1, the eutectic material based on hetero[4]aromatics uses hetero[4]aromatics as an electron donor and 1,2,4,5-tetracyanobenzene as an electron acceptor, with the electron donor and electron acceptor combined in a molar ratio of 1:1.

[0013] In the above technical solution, the hetero[4]aromatic hydrocarbon further has the following general structural formula:

[0014]

[0015] In the above technical solution, further, in step 2, the adsorption temperature is room temperature - 80℃, and the adsorption time is 12-16 hours.

[0016] In the above technical solution, further, in step 2, the molar ratio of the eutectic material based on hetero[4] aromatic hydrocarbons to thiophene is 1:1.

[0017] After the hetero[4]aromatic eutectic material is fully adsorbed in the thiophene vapor atmosphere, the hetero[4]aromatic eutectic material is taken out. Then, the thiophene adsorbed on the surface of the hetero[4]aromatic eutectic material can be removed by vacuum heating or reduced pressure heating. The temperature of the vacuum heating or reduced pressure heating is less than 80°C, so as to realize the regeneration of the hetero[4]aromatic eutectic material.

[0018] In another aspect, the present invention provides a photothermal conversion material prepared by the above-described preparation method.

[0019] The beneficial effects of this invention are as follows:

[0020] The preparation process of this invention uses readily available raw materials, which reduces the preparation cost and simplifies the preparation steps, making the synthesis of the photothermal conversion material more economical and efficient. This helps to improve the feasibility and scalability of the preparation, laying the foundation for large-scale production and commercial application.

[0021] This invention allows for flexible adjustment of photothermal performance by regulating the thiophene vapor adsorption time, thereby increasing its applicability and versatility.

[0022] The photothermal conversion material prepared by this invention achieves efficient photothermal conversion, rapidly and effectively converting light energy into heat energy. It exhibits good stability, long-term reliable performance under different environmental conditions, and excellent photothermal sensitivity. Attached Figure Description

[0023] Figure 1 The PXRD diagrams are of the photothermal conversion material and the eutectic material based on hetero[4]aromatics prepared in Example 1;

[0024] Figure 2 Thermogravimetric analysis (TGA) of the photothermal conversion material prepared in Example 1;

[0025] Figure 3 The single-crystal structure of the photothermal conversion material prepared in Example 1 is shown in a front view, a top view, and c side view.

[0026] Figure 4 The electron spin resonance spectra of TP, H-TCNBα, and H-TCNB@TP in Test Example 1;

[0027] Figure 5 The results of photothermal testing of H-TCNBα under 660nm laser irradiation for three heating-cooling cycles in Test Example 1;

[0028] Figure 6 The results of photothermal testing of H-TCNB@TP under 660nm laser irradiation for three heating-cooling cycles in Test Example 1;

[0029] Figure 7 The image shows the H-TCNBα in Test Example 1 after 10 minutes of 660nm laser irradiation;

[0030] Figure 8 The thermal image of H-TCNB@TP in Test Example 1 after 10 minutes of 660nm laser irradiation;

[0031] Figure 9The heating and freezing curves of H-TCNBα under different powers of 660nm laser in Test Example 2 are shown.

[0032] Figure 10 The heating and freezing curves of H-TCNB@TP under different power 660nm lasers are shown in Test Example 2. Detailed Implementation

[0033] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0034] Unless otherwise specified, the materials used in the embodiments of the present invention can be obtained commercially or prepared according to conventional methods known to those skilled in the art.

[0035] Unless otherwise specified, the operating methods in the following examples are generally performed under conventional conditions or as recommended by the manufacturer.

[0036] Example 1

[0037] (1) The eutectic material based on hetero[4] aromatic hydrocarbons (disclosed in patent CN116606196A) was activated at 120°C for 9 hours;

[0038] (2) Take a 20mL culture bottle, add 1mL of thiophene (TP), take 200mg of activated hetero[4]aromatic eutectic material (named H-TCNBα) and place it in a 5mL open culture bottle. Place the open 5mL culture bottle in the 20mL culture bottle, seal the 20mL culture bottle, and place it in a 25℃ water bath for 16h for adsorption. The hetero[4]aromatic eutectic material changes from orange to black (named H-TCNB@TP).

[0039] In this embodiment, the preparation of the eutectic material based on hetero[4] aromatic hydrocarbons is as follows: 2g of hetero[4] aromatic hydrocarbons and 0.5g of 1,2,4,5-tetracyanobenzene are weighed and placed in 20mL of n-hexane, heated to boiling, and n-hexane is added dropwise until completely dissolved. The solution is stored at 0℃ overnight, the precipitated crystals are collected by filtration, and the obtained crystals are dried under vacuum at 50℃ to obtain the eutectic material based on hetero[4] aromatic hydrocarbons.

[0040] The characterization data of the product prepared in this embodiment are as follows:

[0041] H-TCNB@TP, 1H NMR (600MHz, CDCl3, 293K) (ppm): 8.24 (s, 2H), 7.36 (d, J = 10Hz, 2H), 7.24 (d, J = 10Hz, 4H), 7.14 (d, J = 10Hz, 2H), 6.85 (d, J = 10Hz, 4H), 6.63 (s, 2H ),5.71(s,2H),4.51(s,2H),4.47(s,2H),3.99(s,12H),3.95–3.93(m,4 H), 3.91–3.88 (m, 4H), 3.70 (s, 2H), 3.66 (s, 2H), 1.24 (t, J = 15Hz, 12H).

[0042] 1 H NMR results showed that the eutectic material based on hetero[4] aromatics adsorbed thiophene in a stoichiometric ratio of 1:1.

[0043] PXRD test results and color changes are as follows: Figure 1 As shown, the PXRD pattern obtained after thiophene adsorption is significantly different from the PXRD pattern before adsorption, indicating that thiophene has been adsorbed by the hetero[4]aromatic eutectic material and its crystal form has changed. Furthermore, due to the rearrangement of the crystal structure, the color of the eutectic material after thiophene adsorption has changed from orange to black.

[0044] TG test results as follows Figure 2 As shown, H-TCNB@TP begins to decrease at 100℃, indicating that this eutectic material has good stability at room temperature.

[0045] The single-crystal structure of the photothermal conversion material obtained by adsorbing thiophene onto the eutectic material of hetero[4] aromatic hydrocarbons is as follows: Figure 3 As shown, it can be found that the eutectic material of hetero[4]arene adsorbs thiophene through non-covalent bonds (C–H···π; C–H···O) without changing the chemical composition of the eutectic material of hetero[4]arene and thiophene.

[0046] Test Example 1

[0047] Appropriate amounts of H-TCNBα and H-TCNB@TP were dissolved in water to prepare a 3.0 mM aqueous solution. The solution was then irradiated with a 660 nm laser at a power of 0.7 W / cm². 2 The heating time was 20 min and the cooling time was 20 min. The experiment was repeated 3 times. The differences in infrared thermal images caused by the increase of irradiation time were measured by an infrared thermal imager.

[0048] Electron spin resonance spectrum at room temperature, such as Figure 4As shown, the eutectic material based on hetero[4] aromatics and the thiophene liquid have almost no unpaired electrons. However, after the eutectic material based on hetero[4] aromatics adsorbs thiophene, the new eutectic material formed has a strong spin resonance signal, indicating that there are unpaired electrons in the material.

[0049] At 660nm laser (0.7W cm -2 Photothermal studies of H-TCNBα and H-TCNB@TP under irradiation for three heating-cooling cycles were conducted. The laser was turned off after 20 minutes of irradiation in each cycle. The results are as follows: Figure 5 As shown in Figure 6, this result indicates that H-TCNB@TP has a higher photothermal conversion efficiency than H-TCNBα, and the photothermal conversion material exhibits good photothermal stability. Calculations show that under the laser irradiation conditions, the photothermal conversion efficiency of H-TCNBα is 35.2%, while that of H-TCNB@TP is 72.5%, which is superior to most photothermal conversion agents.

[0050] Infrared thermal images of H-TCNBα and H-TCNB@TP are as follows: Figure 7 As shown in Figure 8, the results show the temperature rise and thermal diffusion in the solution during laser irradiation, indicating that the temperature rise of H-TCNB@TP is faster than that of H-TCNBα, and the diffusion degree is higher, indicating that H-TCNB@TP has a higher heat transfer rate.

[0051] Test Example 2

[0052] H-TCNBα and H-TCNB@TP were irradiated with 690nm lasers of different powers, with laser powers of 0.5 W / cm². 2 0.6w / cm 2 and 0.7w / cm 2 The heating time was 20 minutes, and the cooling time was 20 minutes. The experiment was conducted three times.

[0053] The heating and freezing curves of H-TCNBα and H-TCNB@TP under different powers of 690nm lasers are as follows: Figure 9 As shown in Figure 10, the results indicate that the heating of H-TCNB@TP exhibits a power density-dependent photothermal effect under different near-infrared excitation powers, suggesting that the photothermal conversion behavior of the eutectic can be tuned by changing the excitation power. However, for H-TCNBα, changes in the near-infrared excitation power do not cause changes in its photothermal conversion rate. This result indicates that H-TCNB@TP possesses superior photothermal sensitivity.

[0054] The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the implementation. The scope of protection of the present invention should be determined by the scope defined in the claims. Other variations or modifications can be made based on the above description. Obvious variations or modifications derived therefrom are still within the scope of protection of the present invention.

Claims

1. A method for preparing a photothermal conversion material based on supramolecular eutectic, characterized in that, The method includes the following steps: Step 1: Activate the eutectic material based on hetero[4]aromatics; Step 2: Take thiophene and activated hetero[4]aromatic eutectic material, and use the activated hetero[4]aromatic eutectic material to adsorb the gas volatilized from thiophene to prepare the photothermal conversion material; In step 1, the eutectic material based on hetero[4]aromatics uses hetero[4]aromatics as the electron donor and 1,2,4,5-tetracyanobenzene as the electron acceptor, with the electron donor and electron acceptor combined in a molar ratio of 1:1; the hetero[4]aromatics has the following general structural formula: ； In step 2, the molar ratio of the hetero[4]aromatic eutectic material to thiophene is 1:

1.

2. The preparation method according to claim 1, characterized in that, In step 1, the activation temperature is not lower than 120°C and the activation time is not less than 9 hours.

3. The preparation method according to claim 1, characterized in that, In step 2, the adsorption temperature is room temperature - 80°C, and the adsorption time is 12-16 hours.

4. A photothermal conversion material prepared by the preparation method according to any one of claims 1-3.

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