Phenylene-linked metal ruthenium (ii) homogenous linear polymeric material, evaporator and method of preparation and use thereof

Abstract

The application discloses a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, an evaporator and a preparation method and application thereof; an organic ligand infinite bridging new metal center of a structure shown in I is formed to form a phenylene-connected metal ruthenium (II) homogeneous linear polymer material; on the performance, the polymer material has excellent photo-thermal conversion performance while retaining the excellent optical performance of the metal ruthenium (II) complex and combining the structural advantages of the supramolecular MOFs material. Under the irradiation of 2W / cm 2 of 808nm laser, the polymer material can reach a highest temperature of 335.7 DEG C. The evaporator is prepared for a water evaporation process, under the irradiation of 808nm laser, the water evaporation amount is 0.81kg·m ‑2 , the evaporation efficiency is 1.63kg·m ‑2 ·h ‑1 , and the evaporator has excellent water quality purification capacity for salt removal and organic matter removal.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metal organic complex functional materials, and particularly relates to a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, an evaporator and a preparation method and application thereof. BACKGROUND

[0002] Metal ruthenium (II)-polypyridine complexes have attracted extensive attention in the field of functional materials due to their unique optical, electrochemical and catalytic properties. With the in-depth research, polymer materials based on metal ruthenium (II) have gradually become a research hotspot. At present, the research on metal ruthenium (II) polymers mainly includes two directions: one is to load metal ruthenium (II) complexes as functional groups into metal organic frameworks (MOFs), and to use the high specific surface area and adjustable pore structure of MOFs to improve the stability and functionality of the materials; the other is to use ruthenium (II) and other metals as sub-units to form a bimetallic MOFs system by coordination with organic ligands, and to optimize the performance of the material through the synergistic effect between the metals. However, the research on MOFs synthesized by coordination of single ruthenium (II) as metal center is relatively less, and the existing research is mostly limited to the detection of the optical properties of metal ruthenium (II) complexes, or only focuses on the change of the catalytic performance of MOFs materials, lacking of in-depth exploration of their multifunctionality.

[0003] With the continuous growth of global energy demand and the increasing severity of environmental problems, developing efficient and clean green energy conversion technology has become the focus of current research. Solar energy, as an inexhaustible and inexhaustible renewable energy, its efficient utilization is one of the key ways to solve energy crisis and environmental problems. Photothermal conversion materials can directly convert solar energy into heat energy, and show great application potential in seawater desalination, wastewater treatment, photocatalysis and other fields. However, traditional photothermal conversion materials have low efficiency, poor stability and high cost, which limits their large-scale application. Metal organic framework materials (MOFs) as a new type of porous material, due to their high specific surface area, adjustable pore structure and rich functional sites, show unique advantages in photothermal conversion field.

[0004] Therefore, metal organic framework materials based on metal ruthenium (II) complexes not only have controllable structure, but also have multifunctionality; which provides a new research idea for the application of metal ruthenium (II) polymer materials in photothermal conversion, catalysis and sensing fields. SUMMARY

[0005] Based on the above reasons, the first object of the present application is to provide a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, the homogeneous linear polymer structure formed by the coordination of the ruthenium (II) metal center and the organic ligand; not only has excellent optical properties of the metal ruthenium (II) complex, but also has the structural advantages of the supramolecular MOFs material, further expanding its functionality.

[0006] The second object of the present application is to provide a preparation method of a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, taking the complex of ruthenium (II) and 1,10-phenanthroline as a metal precursor, and directly reacting with an organic ligand to prepare a homogeneous linear polymer material; a simple preparation method is provided.

[0007] The third object of the present application is to provide a phenylene-connected metal ruthenium (II) homogeneous linear polymer material as a light-heat conversion material; the metal ruthenium (II) homogeneous linear polymer of the present application has excellent light-heat conversion performance, and has potential applications in light-heat conversion water evaporation seawater desalination and water purification.

[0008] The fourth object of the present application is to provide an evaporator with excellent water evaporation performance.

[0009] The first object of the present application can be achieved by adopting the following technical scheme:

[0010] A phenylene-connected metal ruthenium (II) homogeneous linear polymer material, two nitrogen atoms on the same phenanthroline in the structure of the organic ligand shown in formula I are coordinated and connected with the same ruthenium atom, and one phenanthroline in each of two adjacent organic ligands shown in formula I is coordinated and connected with one ruthenium atom, respectively.

[0011]

[0012] The second object of the present application can be achieved by adopting the following technical scheme:

[0013] A preparation method of a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, the structure of the organic ligand shown in formula I is reacted with Ru(phen)Cl4 in an organic solvent under an inert gas atmosphere to obtain the phenylene-connected metal ruthenium (II) homogeneous linear polymer material.

[0014] Further, the amount-of-substance ratio of the structure of the organic ligand shown in formula I to Ru(phen)Cl4 is 1:(1-1.2).

[0015] Further, the organic solvent is a mixture of N,N-dimethylformamide and N,N-dimethylacetamide; the molar volume ratio of the organic ligand of formula I to the organic solvent is 1 mmol:(5-50) mL.

[0016] Further, the inert gas atmosphere is a nitrogen or argon atmosphere; the reaction conditions are 120-150 DEG C for 3-24 hours.

[0017] Further, the reaction includes a separation and washing process; after solid-liquid separation, the solid is washed with dimethyl sulfoxide, water and anhydrous ethanol, and vacuum dried at 35-50 DEG C.

[0018] Further, the organic ligand of formula I is prepared by reacting 1,10-phenanthroline-5,6-dione and 1,3-benzenedialdehyde in the presence of an ammonium salt.

[0019] The third object of the present application can be achieved by adopting the following technical solution:

[0020] The application of the phenylene-linked metal ruthenium (II) homogeneous linear polymer material as a photothermal conversion material.

[0021] Further, the phenylene-linked metal ruthenium (II) homogeneous linear polymer material as a photothermal conversion material is used for seawater desalination and wastewater purification.

[0022] The fourth object of the present application can be achieved by adopting the following technical solution:

[0023] An evaporator, which is a Janus evaporator, comprising the phenylene-linked metal ruthenium (II) homogeneous linear polymer material.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] 1. The phenylene-linked metal ruthenium (II) homogeneous linear polymer material of the present application uses ruthenium (II) as a metal center, and new metal centers are bridged by organic ligands to form a homogeneous polymer material; while retaining the excellent optical properties of metal ruthenium (II) complexes, the material combines the structural advantages of supramolecular MOFs materials, effectively expanding the functionality of metal ruthenium (II) complexes.

[0026] 2. The preparation method of the phenylene-linked metal ruthenium (II) homogeneous linear polymer material of the present application, which selects appropriate ruthenium complex precursors and organic ligands for reaction, directly coordinates the organic ligands with the ruthenium complex precursors, and has a simple reaction synthesis route, high yield, efficient and economical preparation method.

[0027] 3. The application of the phenylene-linked metal ruthenium (II) homogeneous linear polymer material, the phenylene-linked metal ruthenium (II) homogeneous linear polymer material has high efficient light-heat conversion capacity and excellent structure stability, and thus can be used as an excellent light-heat conversion material.

[0028] 4. The application of the phenylene-linked metal ruthenium (II) homogeneous linear polymer material to a Janus evaporator, which shows higher water evaporation capacity and evaporation rate; the water evaporation capacity is 0.81 kg·m -2 -2, the evaporation efficiency reaches 1.63 kg·m -2 ·h -1 -2, and the evaporation performance is improved by 228% compared with pure MFS. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 MALDI-TOF-MS spectrum of the ligand bipbz prepared in Example 1;

[0030] Figure 2 ESI-MS spectrum of Ru-phen-bipbz-2 prepared in Comparative Example 1;

[0031] Figure 3 MALDI-TOF-MS spectrum of Ru-phen-bipbz-2 prepared in Comparative Example 1 in the range of 200-2000 m / z;

[0032] Figure 4 MALDI-TOF-MS spectrum of Ru-phen-bipbz-n prepared in Example 2 in the range of 200-2000 m / z;

[0033] Figure 5 MALDI-TOF-MS spectrum of Ru-phen-bipbz-n prepared in Example 2 in the range of 2k-10k m / z;

[0034] Figure 6 XPS analysis diagram of Ru-phen-bipbz-n prepared in Example 2, wherein a is an XPS total spectrum, b is a C1s narrow spectrum, and c is a N1s narrow spectrum;

[0035] Figure 7 XRD diagram of Ru-phen-bipbz-n prepared in Example 2;

[0036] Figure 8 Microscopic morphology diagram of Ru-phen-bipbz-n prepared in Example 2; wherein the left diagram is a SEM diagram, and the right diagram is a TEM diagram;

[0037] Figure 9 EDS elemental distribution diagram of Ru-phen-bipbz-n prepared in Example 2;

[0038] Figure 10 The TG curve for thermal stability analysis of Ru-phen-bipbz-n prepared in Example 2;

[0039] Figure 11 The UV absorption spectra of Ru-phen-bipbz-2 prepared in Comparative Example 1 in different solvents (a) and the UV absorption spectra of Ru-phen-bipbz-n prepared in Example 2 in different solvents (b);

[0040] Figure 12 The solid-state UV-Vis-NIR spectrum of Ru-phen-bipbz-n prepared in Example 2;

[0041] Figure 13 The photothermal performance of Ru-phen-bipbz-n prepared in Example 2 at different power densities is shown in the figure.

[0042] Figure 14 The Ru-phen-bipbz-n prepared in Example 2 was at 1 W / cm 2 The following is a diagram of the photothermal cycle test;

[0043] Figure 15 Real-time photothermal test image of Ru-phen-bipbz-n prepared in Example 2 (808 nm, 1 W / cm²) 2 );

[0044] Figure 16 The water contact angle of the photothermal layer of the Janus evaporator prepared in Example 7;

[0045] Figure 17 Temperature change curve of the Janus evaporator prepared in Example 7 under 808nm laser irradiation;

[0046] Figure 18 The graph shows the change in water evaporation amount with irradiation time when the Janus evaporator prepared in Example 7 is shown in (a); the graph shows the change in evaporation rate with irradiation time is shown in (b).

[0047] Figure 19 The graph shows the change in water evaporation amount with irradiation time when the Janus evaporator prepared in Example 7 is used at different salt concentrations (a); the graph shows the change in evaporation rate with irradiation time (b).

[0048] Figure 20Janus evaporator prepared for example 7 is used at different salt concentrations, evaporator salt removal rate graph (a); evaporator salt removal rate and evaporation rate column chart (b);

[0049] Figure 21 Janus evaporator prepared for example 7 water purification performance graph; Wherein a is the ion concentration comparison graph of seawater before and after desalination; B is the ultraviolet absorption spectrum graph of congo red before and after purification; C is the ultraviolet absorption spectrum graph of methyl orange before and after purification; D is the ultraviolet absorption spectrum graph of methylene blue before and after purification. DETAILED DESCRIPTION

[0050] The technical solutions of the present application will be described below in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0051] The prior art metal ruthenium(II)-polypyridine complex exists in mononuclear or multinuclear, and there is no report on polymer with metal ruthenium(II) as the center and related application. In order to further study the metal ruthenium(II) polymer material, in the preparation, the present application takes ruthenium(II) as the metal center, bridges new metal centers through organic ligand to form homogeneous polymer material; in the performance, the metal ruthenium(II) complex retains excellent optical performance, at the same time, combines the structural advantages of supramolecular MOFs material, further expands its functionality, and optimizes the target performance of the material (such as photo-thermal conversion, catalytic or sensing performance), which provides a new research direction for functional design.

[0052] A phenylene-linked metal ruthenium(II) homogeneous linear polymer material, two nitrogen atoms on the same phenanthroline in the organic ligand shown in formula I are coordinated and connected with the same ruthenium atom, and one phenanthroline in two adjacent organic ligands shown in formula I is respectively coordinated and connected with one ruthenium atom;

[0053]

[0054] Metal ruthenium(II) can be six-coordinated, the organic ligand shown in formula I is used for coordination with metal ruthenium(II), wherein two pyridine nitrogen atoms on the same phenanthroline are coordinated and connected with the same ruthenium atom; two phenanthrolines of one ligand shown in formula I are respectively coordinated with two different metal ruthenium(II). Each metal ruthenium(II) is further coordinated and connected with one phenanthroline on another organic ligand shown in formula I; in this way, the ligand shown in formula I is linearly connected through the coordination of metal ruthenium(II) with the phenanthroline of different ligands shown in formula I.

[0055] As one of the embodiments, each metal ruthenium (II) is further coordinated with two pyridine nitrogen atoms on the phenanthroline ligand. Thus, each metal ruthenium (II) forms a six-coordinated structure.

[0056] As one of the embodiments, the phenylene-linked metal ruthenium (II) homogeneous linear polymer material has a structure shown in formula II:

[0057]

[0058] wherein the bracket is a repeating unit.

[0059] In the present application, by taking ruthenium (II) as the metal center, a new metal center is bridged by an organic ligand to form a homogeneous polymer material; in terms of performance, the metal ruthenium (II) complex retains excellent optical properties while combining the structural advantages of supramolecular MOFs materials to further expand its functionality.

[0060] The present application also provides a preparation method of the phenylene-linked metal ruthenium (II) homogeneous linear polymer material. The formula I structure organic ligand is reacted with Ru(phen)Cl4 in an organic solvent under an inert gas atmosphere to obtain the phenylene-linked metal ruthenium (II) homogeneous linear polymer material.

[0061] The metal ruthenium (II) of the present application is reacted with a Ru(phen)Cl4 precursor containing a phenanthroline ligand. The remaining four coordination sites can be coordinated with the phenanthroline groups of two different formula I structure ligands and extend the coordination in the linear direction; thereby linearly connecting different formula I structure ligands to form a phenylene-linked metal ruthenium (II) homogeneous linear polymer material. The phen in Ru(phen)Cl4 is a 1,10-phenanthroline coordination group.

[0062] As one of the embodiments, the Ru(phen)Cl4 can be purchased or synthesized. When synthesized, RuCl3·H2O is stirred in an aqueous hydrochloric acid solution under an argon atmosphere in the dark, and the reaction is carried out overnight. After post-treatment, the Ru(phen)Cl4 is obtained.

[0063] As one of the embodiments, the formula I structure organic ligand is prepared by reacting 1,10-phenanthroline-5,6-dione and 1,3-benzenedialdehyde in the presence of an ammonium salt.

[0064] The formula I structure organic ligand is prepared by refluxing 1,10-phenanthroline-5,6-dione, 1,3-benzenedialdehyde and ammonium acetate in an acetic acid solution, and then post-treating.

[0065] As one of the embodiments, the molar ratio of the organic ligand with structure shown in formula I to Ru(phen)Cl4 is 1:(1-1.2).

[0066] As one of the embodiments, the organic solvent is a mixture of N,N-dimethylformamide and N,N-dimethylacetamide.

[0067] As one of the embodiments, the molar volume ratio of the organic ligand with structure shown in formula I to the organic solvent is 1 mmol:(5-50)mL.

[0068] As one of the embodiments, the inert gas atmosphere is nitrogen or argon atmosphere; the reaction conditions are 120-150℃ for 3-24h.

[0069] As one of the embodiments, the reaction includes a separation and washing process; after solid-liquid separation, the solid is washed with dimethyl sulfoxide, water, and anhydrous ethanol respectively, and vacuum dried at 35-50℃.

[0070] The application also provides the application of the phenylene-connected metal ruthenium (II) homogeneous linear polymer material as a photothermal conversion material.

[0071] As one of the embodiments, the phenylene-connected metal ruthenium (II) homogeneous linear polymer material is used as a photothermal conversion material for seawater desalination and wastewater purification.

[0072] The application also provides an evaporator, which is a Janus evaporator, and the evaporator comprises the phenylene-connected metal ruthenium (II) homogeneous linear polymer material.

[0073] As one of the embodiments, the evaporator is a Janus evaporator loaded with a melamine sponge and a photothermal material.

[0074] As one of the embodiments, the photothermal material comprises a combination of PDMS precursor, phenylene-connected metal ruthenium (II) homogeneous linear polymer material, and ethyl acetate.

[0075] As one of the embodiments, the PDMS precursor, curing agent, and ethyl acetate are mixed thoroughly; the phenylene-connected metal ruthenium (II) homogeneous linear polymer material is added and further mixed; the melamine sponge is soaked in the resulting mixture, completely absorbed, and vacuum dried to obtain a Janus evaporator loaded with a photothermal material.

[0076] The following is further illustrated with specific examples.

[0077] Synthesis of ligand bipbz in example 1

[0078] To a flask containing 50 mL of acetic acid, 1,10-phenanthroline-5,6-dione 2 mmol, 1,3-benzenedialdehyde 1 mmol and ammonium acetate 20 mmol were added and refluxed at 118 °C for 6 h; after cooling to room temperature, the supernatant was removed by centrifugation and the resulting precipitate was washed with deionized water and anhydrous ethanol until the filtrate was weakly acidic or neutral. Then, the precipitate was refluxed in ethanol at 78 °C for 2 h; after cooling to room temperature, it was suction filtered and the precipitate was washed with deionized water and anhydrous ethanol, vacuum dried at 40 °C for 24 h to obtain the organic ligand of the structure shown in Formula I, named bipbz; yield: 0.41 g, yield: 75%; the results of its MALDI-TOF analysis are shown in Figure 1

[0079] Example 2 Synthesis of linear polymeric Ru-phen-bipbz-n

[0080] To a flask containing 5 mL of N,N-dimethylformamide (DMF), 1 mmol of bipbz prepared in Example 1 and 1.2 mmol of Ru(phen)Cl4 were added and reacted at 120 °C for 18 h under a nitrogen atmosphere, cooled to room temperature, diluted with deionized water, suction filtered and the precipitate was washed with dimethyl sulfoxide (DMSO), water and anhydrous ethanol, respectively, vacuum dried at 40 °C for 24 h to obtain the phenylene- linked metal ruthenium (II) homogeneous linear polymeric material.

[0081] Example 3

[0082] To a flask containing 5 mL of N,N-dimethylformamide (DMF), 1 mmol of bipbz prepared in Example 1 and 1.2 mmol of Ru(phen)Cl4 were added and reacted at 120 °C for 18 h under a nitrogen atmosphere, cooled to room temperature, diluted with deionized water, suction filtered and the precipitate was washed with dimethyl sulfoxide (DMSO), water and anhydrous ethanol, respectively, vacuum dried at 40 °C for 24 h to obtain the phenylene- linked metal ruthenium (II) homogeneous linear polymeric material.

[0083] Example 4

[0084] ​To a flask containing 10 mL of N,N-dimethylformamide (DMF) was added 1 mmol of bipbz prepared in example 1 and 1.05 mmol of Ru(phen)Cl4 and reacted at 130 °C for 12 h under nitrogen atmosphere, cooled to room temperature, diluted with deionized water, suction filtered and the precipitate was washed with dimethyl sulfoxide (DMSO), water and absolute ethanol respectively, vacuum dried at 40 °C for 24 h to obtain the phenylene linked metal ruthenium (II) homogenous linear polymeric material.

[0085] Example 5

[0086] To a flask containing 50 mL of N,N-dimethylacetamide (DMAC) was added 1 mmol of bipbz prepared in example 1 and 1.15 mmol of Ru(phen)Cl4 and reacted at 140 °C for 3 h under nitrogen atmosphere, cooled to room temperature, diluted with deionized water, suction filtered and the precipitate was washed with dimethyl sulfoxide (DMSO), water and absolute ethanol respectively, vacuum dried at 40 °C for 24 h to obtain the phenylene linked metal ruthenium (II) homogenous linear polymeric material.

[0087] Example 6

[0088] To a flask containing 15 mL of N,N-dimethylformamide (DMF), 15 mL of N,N- dimethylacetamide (DMAC) was added 1 mmol of bipbz prepared in example 1 and 1.1 mmol of Ru(phen)Cl4 and reacted at 150 °C for 24 h under nitrogen atmosphere, cooled to room temperature, diluted with deionized water, suction filtered and the precipitate was washed with dimethyl sulfoxide (DMSO), water and absolute ethanol respectively, vacuum dried at 40 °C for 24 h to obtain the phenylene linked metal ruthenium (II) homogenous linear polymeric material.

[0089] Comparative example 1 Dinuclear complex

[0090] To a flask containing 30 mL of ethylene glycol was added 1 mmol of bipbz prepared in example 1 and 2 mmol of Ru(phen)2Cl2 and refluxed at 120 °C for 8 h under nitrogen atmosphere; cooled to room temperature, diluted with deionized water, saturated ammonium hexafluorophosphate solution was added to completely precipitate the product, suction filtered and the precipitate was washed with deionized water thoroughly, vacuum dried at 40 °C for 24 h to obtain the dinuclear complex Ru-phen-bipbz-2; yield: 1.34 g, yield: 85%; structure is:

[0091] ESI-MS analytical spectrum is shown in Figure 2 ; wherein ESI-MS (MeCN): m / z = 478.32 ([M-4PF6-H] 3+MALDI-TOF analysis spectrum as shown Figure 3 As shown; the following ion source fragment can be identified through simulation: 460.218([Ru(phen)2]) 2+ [MH] + ), 497.202([Ru(phen)2Cl] + ,[M]+), 532.185([Ru(phen)2Cl2],[M]), 615.295([Ru(bipbzH)] 2+ [MH] + )、894.356([Ru2(phen)(bipbzH)] 4+ [M-3H] + )、975.561([Ru(phen)2(bipbzH)] 2+ [MH] + ).

[0092] Structural characterization:

[0093] 1. The Ru-phen-bipbz-n prepared in the examples was analyzed by MALDI-TOF. The MALDI-TOF-MS spectra in the range of 200 to 2000 Da are shown below. Figure 4 As shown; the MALDI-TOF-MS spectra in the range of 2kDa to 10kDa are as follows. Figure 5 As shown.

[0094] Due to the poor solubility of the Ru-phen-bipbz-n polymer material, its molecular weight was characterized using MALDI-TOF-MS. MALDI-TOF-MS spectra in the range of 200 to 2000 Da are shown below. Figure 4 The results show that Ru-phen-bipbz-n has obvious fragment peaks. These fragment peaks are highly similar to the MALDI-TOF test results of its corresponding binuclear complex (Comparative Example 1) under the same experimental conditions. Simulation of these peaks can also identify the peak attribution.

[0095] Specifically, in the spectrum of Ru-phen-bipbz-n Figure 4 In the fragment signals with m / z = 460.470, 497.009, 515.217, 615.121, 796.136, 831.109, 1128.244, 1165.207, and 1309.292, the fragment signals are attributed to the following ion: [Ru(phen)2-H] + [Ru(phen)2Cl] + [bipbz+H] +[Ru(bipbzH)-H] + [Ru(phen)(bipbzH2)-H] + [Ru(phen)(bipbzH)Cl] + [Ru(bipbz)2-H] + [Ru(bipbz)(bipbzH)Cl] + [Ru(phen)(bipbz)(bipbzH)-H] + .

[0096] In the analysis of Ru-phen-bipbz-n in the high molecular weight region of 2 kDa to 10 kDa, some significant peaks were observed, corresponding to different peak values of polymerization degree, respectively: m / z = 2107.43 ([Ru2(phen)2(bipbzH2)3] 4+ , [M-3H] + ), 2900.42 ([Ru3(phen)3(bipbz)(bipbzH2)3] 6+ , [M-5H] + ) and 3697.37 ([Ru4(phen)4(bipbzH2)5] 8+ , [M-7H] + ). These results show that polymers of different polymerization degrees can be detected, and also show that the final product is a multi-component polymer containing different polymerization degrees.

[0097] 2, the Ru-phen-bipbz-n prepared by the example was analyzed by XPS to analyze the surface chemical state, and the results are shown in Figure 6 , where a is the XPS total spectrum; b is the C1s narrow spectrum; c is the N1s narrow spectrum.

[0098] C, O, N and Ru elements can be detected in Ru-phen-bipbz-n, indicating that the material preparation is successful; the narrow spectrum shows that the C1s and N1s peaks of the polymer are shifted to a higher binding energy direction. This may be because the metal ruthenium (II) linear polymer can continuously extend the chain length at both ends of the organic ligand, and in the process of polymerization, the overall content of the auxiliary ligand phenanthroline (phen) with lower binding energy will decrease with the increase of the chain length, eventually leading to the binding energy of Ru (II) linear polymer material moving to the high binding energy direction.

[0099] 3, the Ru-phen-bipbz-n prepared by the example was tested by XRD, and the results are shown in Figure 7 .

[0100] The XRD pattern of Ru-phen-bipbz-n shows several more clear and sharp diffraction peaks, indicating that Ru-phen-bipbz-n has a more ordered crystallinity.

[0101] 4. Micro-morphology test was performed on the Ru-phen-bipbz-n prepared in the example, the SEM image is shown in the left of Figure 8 ; the TEM image is shown in the right of Figure 8 ; and the EDS image is shown in Figure 9 .

[0102] Ru-phen-bipbz-n presents a compact lamellar crystal structure, small size and overall uniform distribution, indicating that it has good crystallinity and more uniform morphology. The TEM image further indicates that Ru-phen-bipbz-n presents a lamellar stacked morphology structure, indicating that the sample has a high degree of order and good crystallinity. EDS element analysis shows that Ru, N and C are uniformly distributed in Ru-phen-bipbz-n, and the distribution of N and C elements is consistent with the structure of the organic ligand, further confirming the effective combination of the organic ligand and the metal center.

[0103] 5. Thermal stability analysis was performed on the Ru-phen-bipbz-n prepared in the example, and the thermogravimetric analysis (TGA) test results are shown in Figure 10 .

[0104] The mass loss of Ru-phen-bipbz-n at 300℃ is only 4.42%, and the mass loss at 800℃ is 34.59%. These results show that Ru-phen-bipbz-n material exhibits good thermal stability, indicating that the coordination between Ru(II) center and ligand is relatively stable, and can maintain the stability of the skeleton structure at high temperature.

[0105] The organic ligand bipbz of Ru-phen-bipbz-n has a meta-connected phenyl ring structure, which makes the molecular packing more compact, thereby improving the overall thermal stability of the material.

[0106] 6. UV absorption analysis was performed on the Ru-phen-bipbz-n prepared in the example and the Ru-phen-bipbz-2 prepared in the comparative example 1, and UV-Vis absorption spectrum test was performed on 20 μg / mL of Ru-phen-bipbz-n and Ru-phen-bipbz-2 in dichloromethane, ethanol, water, acetonitrile and acetone, respectively; the results are shown in Figure 11Ru-phen-bipbz-2 and b is Ru-phen-bipbz-n. The solid UV-Vis-NIR test was performed on Ru-phen-bipbz-n, and the spectrum is shown in FIG. 2. Figure 12

[0107] The results show that the binuclear complex of Comparative Example 1 and the linear polymer of the embodiment both exhibit similar ultraviolet absorption peaks. However, compared with the binuclear complex, the absorption peaks of the linear polymer at 275 nm, 360 nm and 460 nm are relatively weak. This change is related to the structural characteristics of the linear polymer of metal ruthenium (II). During the polymerization process, as the length of the polymer chain increases, the content of the ligand phen gradually decreases, so the absorption band at 275 nm caused by the π-π* transition of the phen part is significantly weakened. At the same time, due to the relative increase in the content of the organic ligand bipbz during the polymerization process, it further promotes the charge transfer of the ligand itself, thereby enhancing the absorption band at 360 nm. In addition, the absorption band at 460 nm caused by the MLCT transition is also weakened due to the decrease in the ratio of phen and metal center, resulting in the absorption peak of the linear polymer at this wavelength being lower than that of the corresponding binuclear complex. The solid UV-Vis-NIR absorption test results of Ru-phen-bipbz-n show that the polymerization material has effective absorption in the near-infrared spectral range, indicating that it has potential applications in the near-infrared region.

[0108] Example 7

[0109] The PDMS precursors Sylgard 184a, Sylgard 184b and ethyl acetate were mixed in a mass ratio of 0.25:0.25:10; the volume of the mixture was 10 mL, 10 mg of Ru-phen-bipbz-n prepared in Example 1 was added and further mixed by ultrasonic dispersion; the melamine sponge (MFS) was soaked in the resulting mixture until the solution was completely absorbed, and Ru-phen-bipbz-n was adsorbed on the surface of MFS. Finally, the MFS was vacuum dried at 80°C for 3h to prepare a Janus evaporator loaded with Ru-phen-bipbz-n.

[0110] Comparative Example 2

[0111] Comparative Example 2 differs from Example 7 in that Ru-phen-bipbz-2 prepared in Comparative Example 1 is used instead of Ru-phen-bipbz-n prepared in Example 1, and the other steps are the same.

[0112] Performance test:

[0113] 1. Photothermal conversion ability test ​

[0114] The Ru-phen-bipbz-n prepared in the example and the Ru-phen-bipbz-2 prepared in the comparative example 1 were tested under 808 nm laser irradiation at different power densities, and the surface maximum temperature change of the Ru-phen-bipn-n powder was as shown in Figure 13 The cyclic photothermal experiment was carried out at 1 W / cm 2 The surface maximum temperature change of the Ru-phen-bipn-n powder was as shown in Figure 14 The infrared thermal imaging instrument actually photographed the effect of one photothermal cycle was as shown in Figure 15 .

[0115] Under 808 nm laser irradiation, the surface temperature of the polymer powder sample rapidly rose within 5 seconds. After the laser was turned off, the temperature of the sample rapidly returned to room temperature within 10 seconds. With the increase of the laser power density, the maximum temperature that the surface of the material could reach rose, showing a clear positive correlation between the laser power density. Under 808 nm laser irradiation at 2 W / cm 2 The surface maximum temperature of the Ru-phen-bipbz-n powder reached 335.7°C.

[0116] In order to further test the stability of the photothermal conversion of the material, the sample was subjected to cyclic photothermal experiment at 1 W / cm 2 After five cycles of testing, the Ru-phen-bipbz-n still maintained stable and rapid photothermal response, and its photothermal performance hardly lost. During the long-time laser irradiation process, the sample did not show obvious photobleaching phenomenon, which further verified its excellent photothermal stability. The above experimental results showed that these materials had good photothermal conversion efficiency and stability, and could be well applied in the fields of energy conversion and storage.

[0117] 2. Water evaporation capacity test

[0118] The Ru-phen-bipbz-n was loaded on the photothermal coating of the Janus evaporator to explore its effect in the field of water evaporation actual application. Commercially available hydrophilic melamine foam (MFS) was selected as the evaporator platform, and the photothermal material was solidified on the top end of the MFS through a curing agent. The thickness of the photothermal material fixedly loaded was 5 mm, and the total loading amount of the photothermal material was 10 mg. A Janus evaporator containing photothermal material on the top end and blank MFS on the bottom end was constructed.

[0119] The contact angle of the photothermal material layer of the Janus evaporator loaded with Ru-phen-bipbz-n was 104.8° Figure 16The bottom retains the hydrophilicity of the MFS (Metal-Film-Semiconductor-Fluorescent) material, consistent with the Janus evaporator's design philosophy of hydrophobic top and hydrophilic bottom. This ensures efficient water transport from the bottom layer to the photothermal material layer for evaporation while also enhancing the overall heat dissipation performance of the evaporator. Photothermal conversion performance tests were conducted on the Janus evaporator under 808nm laser irradiation. The results showed that the power density under 808nm laser irradiation was 1W / cm². 2 At that time, the Janus evaporator surface temperature responded rapidly within 10 seconds and reached steady state within 60 seconds, which met our design expectations. The Ru-phen-bipbz-n evaporator reached 163.4℃, compared to only 26.4℃ for pure MFS. Figure 17 This indicates that the Janus evaporator prepared in this application has a faster response and a more efficient photothermal conversion capability under 808nm laser irradiation.

[0120] The bottom of the evaporator was immersed in water, and the photothermal material layer was irradiated with an 808nm laser. Simultaneously, the mass loss of water and the corresponding evaporation rate were recorded. The change in water evaporation over time is shown in the figure below. Figure 18 As shown in Figure a; the evaporation rate changes with irradiation time as follows: Figure 18 As shown in b.

[0121] like Figure 18 As shown, the water evaporation rate of pure MFS under 808nm laser irradiation is only 0.25 kg·m³. -2 The evaporation efficiency is 0.50 kg·m³. -2 ·h -1 In contrast, the Janus evaporator loaded with the photothermal material Ru-phen-bipbz-n exhibited a higher water evaporation rate and a water evaporation capacity of 0.81 kg·m³. -2 The evaporation efficiency is 1.63 kg·m³. -2 ·h -1 Compared to pure MFS, the evaporation performance is improved by 228%, which is a very considerable result.

[0122] To evaluate the salt precipitation resistance of the Janus evaporator under high water evaporation rates, the effect of different mass concentrations (0%, 5.0%, 10.0%, and 15.0% wt%) of NaCl solution on the evaporation performance of the Janus evaporator was investigated. The water evaporation rate of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations over time is shown in the figure below. Figure 19 As shown in Figure a; the evaporation rate of the Janus evaporator loaded with Ru-phen-bipbz under different NaCl concentrations varies with irradiation time as shown in Figure a. Figure 19As shown in Figure b; the desalination rate of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations is as follows: Figure 20 As shown in Figure a; the desalination rate and evaporation rate of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations are shown in Figure a. Figure 20 As shown in b.

[0123] from Figure 19 It can be seen that the Janus evaporator loaded with Ru-phen-bipbz-n has a water evaporation rate of 0.69 kg·m³ when evaporating a 5% NaCl solution. -2 The evaporation efficiency was 1.3832 ± 0.02346 kg·m³. -2 ·h -1 When evaporating a 15% NaCl solution, the water evaporation rate is 0.51 kg·m³. -2 The evaporation efficiency was 1.0175 ± 0.03887 kg·m³. -2 ·h -1 The test data above show that the Janus evaporator loaded with Ru-phen-bipbz-n exhibits a decreasing evaporation performance with increasing NaCl concentration across different mass concentration gradients. We speculate that this result may be due to the partial adsorption of NaCl crystals into the interior of the Janus evaporator during evaporation, thus hindering water transport.

[0124] Even so, the Janus evaporator described above showed significantly better evaporation performance than the pure MFS in tests involving the evaporation of 15% NaCl solution. Furthermore, from... Figure 20 It can be seen that the desalination rate of NaCl solutions with different mass concentrations all exceeded 99.5%. Notably, no salt crystallization was observed throughout the experiment. These results demonstrate that the prepared Janus evaporator exhibits excellent water evaporation performance and superior salt resistance even under high salinity conditions, highlighting its potential in the field of efficient seawater desalination.

[0125] 3. Water purification capacity test

[0126] A simulation experiment of the actual seawater desalination process was conducted using the Janus evaporator prepared in Example 7. The experimental results showed that the four main ions (Na+, Na ... + Mg 2+ Ca 2+ K + The concentration of [a specific substance] in the condensate decreased to below 1 ppm after evaporation, significantly lower than the 10-500 ppm achievable by traditional membrane-based reverse osmosis methods. Figure 21 (a) In addition, Ru in water samples before and after evaporation2+ No obvious change in the concentration of Ru(bpy)32+was detected, indicating that the introduction of the photothermal material did not result in the loss of photothermal resources, while Ru 2+ will not leak through the Janus evaporator, thereby avoiding potential harm to water bodies and human health.

[0127] Methyl orange (MO), Congo red (CR) and methylene blue (MB) were selected as model organic pollutants; the Janus evaporator prepared in Example 7 was used to perform water evaporation, and the condensed water was collected during the evaporation process and analyzed by ultraviolet-visible absorption spectroscopy. The results are shown in Figure 21 ; wherein b is CR; c is MO; and d is MB.

[0128] Figure 21 It is shown that the characteristic absorption peaks of MO at 465 nm, CR at 525 nm and MB at 663 nm all completely disappeared in the condensed water sample, indicating that these organic pollutants did not appear in the purified water during the evaporation process.

[0129] In summary, the organic ligand represented by formula I in the application and metal ruthenium (II) construct homogeneous linear polymers, retain the excellent optical properties of metal ruthenium (II) complexes, and combine the structural advantages of supramolecular MOFs materials, so that the polymers realize efficient application in the fields of photothermal conversion, water evaporation and water purification.

[0130] The above embodiments are only preferred embodiments of the application, and cannot be used to limit the scope of protection of the application. Any non-essential changes and substitutions made by those skilled in the art on the basis of the application all belong to the scope of protection required by the application.

Claims

1. The application of a phenylene-linked homogeneous linear ruthenium(II) polymer material as a photothermal conversion material, characterized in that, The phenylene-linked ruthenium(II) homogeneous linear polymer material is as follows: in the organic ligands of Formula I, two nitrogen atoms on the same phenanthroline are coordinated and connected to the same ruthenium atom, and in two adjacent organic ligands of Formula I, one phenanthroline is coordinated and connected to one ruthenium atom. Equation I; The preparation method of the phenylene-linked ruthenium(II) homogeneous linear polymer material is as follows. The organic ligand with the structure shown in Formula I reacts with Ru(phen)Cl4 in an organic solvent under an inert gas atmosphere to obtain the homogeneous linear polymer material of ruthenium(II) linked to phenylene. The molar ratio of the organic ligand shown in Formula I to Ru(phen)Cl4 is 1:(1-1.2). The inert gas atmosphere is a nitrogen or argon atmosphere; the reaction conditions are 120-150℃ for 3-24 hours.

2. The application of the phenylene-linked ruthenium(II) homogeneous linear polymer material of claim 1 as a photothermal conversion material, characterized in that, The organic solvent is one or a mixture of N,N-dimethylformamide and N,N-dimethylacetamide; the molar-volume ratio of the organic ligand with the structure shown in Formula I to the organic solvent is 1 mmol: (5-50) mL.

3. The application of the phenylene-linked homogeneous linear polymer material of ruthenium(II) as a photothermal conversion material according to claim 2, characterized in that, The reaction includes a separation and washing process; after solid-liquid separation, the solid is washed with dimethyl sulfoxide, water, and anhydrous ethanol respectively, and then dried under vacuum at 35-50℃.

4. The application of the phenylene-linked homogeneous linear polymer material of ruthenium(II) as a photothermal conversion material according to claim 2, characterized in that, The organic ligand with the structure shown in Formula I is prepared by reacting 1,10-phenanthroline-5,6-dione and 1,3-benzaldehyde in the presence of an ammonium salt.

5. The application according to claim 1, characterized in that, The phenylene-linked ruthenium(II) homogeneous linear polymer material is used as a photothermal conversion material for seawater desalination and wastewater purification.

6. An evaporator, characterized in that, The evaporator is a Janus evaporator, which comprises the phenylene-linked ruthenium(II) homogeneous linear polymer material as described in claim 1.

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