Phenylene-connected metal ruthenium (II) homogeneous linear polymer material, evaporator and preparation method and application thereof

Abstract

The invention discloses a phenylene-connected metal ruthenium (II) homogeneous linear polymer material, an evaporator and a preparation method and application of the phenylene-connected metal ruthenium (II) homogeneous linear polymer material. An organic ligand with a structure shown as I is infinitely bridged with a new metal center to form a phenylene-connected metal ruthenium (II) homogeneous linear polymeric material; the polymer material has excellent photo-thermal conversion performance by combining the structural advantages of the supramolecular MOFs material while maintaining the excellent optical performance of the metal ruthenium (II) complex. Under the irradiation of 808nm laser of 2W / cm < 2 >, the polymeric material can reach the maximum temperature of 335.7 DEG C. The prepared evaporator is used in the water evaporation process, under 808nm laser irradiation, the water evaporation capacity is 0.81 kg.m <-2 >, the evaporation efficiency is 1.63 kg.m <-2 >. H <-1 >, and the water quality purification capacity of removing salt and organic matter is excellent.

Description

Technical Field

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

[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, ruthenium(II)-based polymeric materials have gradually become a research hotspot. At present, the research on ruthenium(II) polymers mainly focuses on two directions: one is to load ruthenium(II) complexes as functional groups into metal-organic frameworks (MOFs), and utilize 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 together as substructural units to coordinate with organic ligands to form a bimetallic MOF system, and optimize the properties of the materials through the synergistic effect between metals. However, there are relatively few studies on the coordination synthesis of MOFs with ruthenium(II) as the sole metal center, and the existing studies are mostly limited to the detection using the optical properties of ruthenium(II) complexes, or only focus on the transformation of the catalytic properties of MOF materials, lacking in-depth exploration of their multifunctionality.

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

[0004] Therefore, metal-organic framework materials based on ruthenium(II) complexes can not only achieve structural controllability but also have multifunctionality, providing new research ideas for the application of ruthenium(II) polymeric materials in fields such as photothermal conversion, catalysis, and sensing. Summary of the Invention

[0005] For the above reasons, the first object of the present invention is to provide a phenylene-linked ruthenium(II) homogeneous linear polymer material, in which the ruthenium(II) metal center coordinates with an organic ligand to form a homogeneous linear polymer structure; it not only has excellent optical properties of ruthenium(II) complexes, but also has the structural advantages of supramolecular MOFs materials, further expanding its functionality.

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

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

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

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

[0010] A phenylene-linked ruthenium(II) homogeneous linear polymer material, in which two nitrogen atoms on the same phenanthroline of the organic ligand shown in formula I coordinate and connect with the same ruthenium atom, and one phenanthroline on two adjacent organic ligands shown in formula I respectively coordinates and connects with a ruthenium atom;

[0011]

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

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

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

[0015] Further, 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.

[0016] Further, the inert gas atmosphere is a nitrogen or argon atmosphere; the reaction conditions are to react at 120 - 150 °C for 3 - 24 h.

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

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

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

[0020] Application of the phenyl-linked ruthenium(II) homogeneous linear polymer material as a photothermal conversion material.

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

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

[0023] An evaporator, the evaporator is a Janus evaporator, and the evaporator includes the phenyl-linked ruthenium(II) homogeneous linear polymer material.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] 1. For the phenyl-linked ruthenium(II) homogeneous linear polymer material of the present invention, ruthenium(II) is used as the metal center, and new metal centers are infinitely bridged through organic ligands to form a homogeneous polymer material; while retaining the excellent optical properties of ruthenium(II) complexes, the structural advantages of supramolecular MOFs materials are combined to effectively expand the functionality of ruthenium(II) complexes.

[0026] 2. For the preparation method of the phenyl-linked ruthenium(II) homogeneous linear polymer material of the present invention, a suitable ruthenium complex precursor and an organic ligand are selected for reaction, and the organic ligand is directly coordinated and connected with the ruthenium complex precursor. The reaction synthesis route is simple, the yield is high, and the preparation method is efficient and economical.

[0027] 3. Application of the phenyl group-linked ruthenium (II) homogeneous linear polymer material of the present invention. The phenyl group-linked ruthenium (II) homogeneous linear polymer material of the present invention has high efficient photothermal conversion ability and excellent structural stability, and thus can be used as an excellent photothermal conversion material.

[0028] 4. An evaporator of the present invention, which is a Janus evaporator loaded with the phenyl group-linked ruthenium (II) homogeneous linear polymer material of the present application, showing a higher water evaporation amount and evaporation rate; the water evaporation amount is 0.81 kg·m -2 , and the evaporation efficiency reaches 1.63 kg·m -2 ·h -1 , and the improvement amplitude of the evaporation performance compared with that of pure MFS is 228%. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

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

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

[0036] Figure 8 is the microscopic morphology diagram of Ru-phen-bipbz-n prepared in Example 2; the left figure is the SEM diagram; the right figure is the TEM diagram;

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

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

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

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

[0041] Figure 13 Photothermal performance diagram of Ru-phen-bipbz-n prepared in Example 2 under different power densities;

[0042] Figure 14 For Ru-phen-bipbz-n prepared in Example 2 at 1 W / cm 2 Photothermal cycling test diagram;

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

[0044] Figure 16 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 808 nm laser irradiation;

[0046] Figure 18 When the Janus evaporator prepared in Example 7 is in use, diagram of the change in water evaporation amount with irradiation time (a); diagram of the change in evaporation rate with irradiation time (b);

[0047] Figure 19 When the Janus evaporator prepared in Example 7 is in use under different salt concentrations, diagram of the change in water evaporation amount with irradiation time (a); diagram of the change in evaporation rate with irradiation time (b);

[0048] Figure 20Desalination rate graph (a) of the Janus evaporator prepared in Example 7 when used at different salt concentrations; bar graph (b) of the desalination rate and evaporation rate of the evaporator.

[0049] Figure 21 Water purification performance graph of the Janus evaporator prepared in Example 7; where a is the comparison graph of ion concentrations 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 implementation manners

[0050] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only partial embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0051] The metal ruthenium (II)-polypyridine complexes of the prior art exist in the form of mononuclear or polynuclear, and there are no reports on polymers centered on metal ruthenium (II) and related applications. In order to further study metal ruthenium (II) polymer materials, in the preparation of this application, ruthenium (II) is used as the metal center, and new metal centers are infinitely bridged through organic ligands to form homogeneous polymer materials; in terms of performance, while retaining the excellent optical properties of metal ruthenium (II) complexes, the structural advantages of supramolecular MOFs materials are combined to further expand their functionality; the target properties of the materials (such as photothermal conversion, catalytic or sensing properties) are optimized to provide a new research direction for functional design.

[0052] A phenylene-linked metal ruthenium (II) homogeneous linear polymer material, in which two nitrogen atoms on the same phenanthroline in the organic ligand shown in Formula I are coordinately connected to the same ruthenium atom, and one phenanthroline in two adjacent organic ligands shown in Formula I is respectively coordinately connected to a ruthenium atom.

[0053]

[0054] Metal ruthenium (II) can be hexacoordinated at the center. In this application, the organic ligand shown in Formula I is used to coordinate with metal ruthenium (II), and two pyridine nitrogen atoms on the same phenanthroline are coordinately connected to the same ruthenium atom; the two phenanthrolines of one ligand shown in Formula I are respectively coordinated with two different metal ruthenium (II). Each metal ruthenium (II) is also coordinately connected to one phenanthroline on another organic ligand shown in Formula I; in this way, through the coordination connection of metal ruthenium (II) with the phenanthrolines of different ligands shown in Formula I, the ligands shown in Formula I are linearly connected.

[0055] As one of the embodiments, each ruthenium(II) metal is also coordinatively connected to two pyridine nitrogen atoms on a phenanthroline ligand. Thus, each ruthenium(II) metal forms a six-coordinate structure.

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

[0057]

[0058] Wherein, the content in the brackets is the repeating unit.

[0059] In this application, by using ruthenium(II) as the metal center and infinitely bridging new metal centers through organic ligands, a homogeneous polymer material is formed; in terms of performance, while retaining the excellent optical properties of ruthenium(I I) metal complexes, the structural advantages of supramolecular MOFs materials are combined to further expand their functionality.

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

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

[0062] As one of the embodiments, Ru(phen)Cl4 can be purchased or synthesized. When synthesizing, RuCl3·H2O is in an aqueous hydrochloric acid solution, and reacts with 1,10-phenanthroline under an argon atmosphere and stirs in the dark, and then reacts overnight, and the Ru(phen)Cl4 is obtained after post-treatment.

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

[0064] 1,10-phenanthroline-5,6-dione, 1,3-benzenedicarboxaldehyde and ammonium acetate are refluxed in an acetic acid solution, and the organic ligand shown in Formula I is prepared after post-treatment.

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

[0066] As one of the embodiments, the organic solvent is one or 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 the 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 a nitrogen or argon atmosphere; the reaction conditions are to react at 120 - 150 °C for 3 - 24 h.

[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 absolute ethanol respectively, and vacuum dried at 35 - 50 °C.

[0070] This application also provides the use of the phenyl-linked ruthenium(II) homogeneous linear polymer material as a photothermal conversion material.

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

[0072] This application also provides an evaporator, which is a Janus evaporator and includes the phenyl-linked ruthenium(II) homogeneous linear polymer material.

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

[0074] As one of the embodiments, the photothermal material includes a composition of a PDMS precursor, a phenyl-linked ruthenium(II) homogeneous linear polymer material, and ethyl acetate.

[0075] As one of the embodiments, the PDMS precursor, curing agent, and ethyl acetate are fully mixed; the phenyl-linked ruthenium(II) homogeneous linear polymer material is added for further mixing; the melamine sponge is immersed in the obtained mixed solution, fully absorbed, and vacuum dried to obtain a Janus evaporator loaded with a photothermal material.

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

[0077] Example 1 Synthesis of Ligand bipbz

[0078] 2 mmol of 1,10-phenanthroline-5,6-dione, 1 mmol of 1,3-benzenedicarboxaldehyde and 20 mmol of ammonium acetate were added to a flask containing 50 mL of acetic acid, and the mixture was refluxed at 118 °C for 6 h. After cooling to room temperature, the supernatant was removed by centrifugation, and the obtained precipitate was washed with deionized water and absolute ethanol until the pH of 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, the precipitate was filtered by suction and washed with deionized water and absolute ethanol. The precipitate was dried in vacuo at 40 °C for 24 h to obtain an organic ligand with the structure shown in Formula I, named bipbz; yield: 0.41 g, yield rate: 75%; the MALDI-TOF analysis result was as Figure 1 shown; the mass-to-charge ratio of the main peak was 515.07.

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

[0080] 1 mmol of bipbz prepared in Example 1 and 1 mmol of Ru(phen)Cl4 were added to a flask containing 20 mL of N,N-dimethylformamide (DMF), and the reaction was carried out at 150 °C for 6 h under a nitrogen atmosphere. After cooling to room temperature, it was diluted with deionized water, filtered by suction, and the precipitate was washed with dimethyl sulfoxide (DMSO), water and absolute ethanol respectively, and dried in vacuo at 40 °C for 24 h to obtain the phenyl-linked ruthenium(II) homogeneous linear polymer material, named Ru-phen-bipbz-n; yield: 0.74 g, yield rate 80%.

[0081] Example 3

[0082] 1 mmol of bipbz prepared in Example 1 and 1.2 mmol of Ru(phen)Cl4 were added to a flask containing 5 mL of N,N-dimethylformamide (DMF), and the reaction was carried out at 120 °C for 18 h under a nitrogen atmosphere. After cooling to room temperature, it was diluted with deionized water, filtered by suction, and the precipitate was washed with dimethyl sulfoxide (DMSO), water and absolute ethanol respectively, and dried in vacuo at 40 °C for 24 h to obtain the phenyl-linked ruthenium(II) homogeneous linear polymer material.

[0083] Example 4

[0084] 1 mmol of bipbz prepared in Example 1 and 1.05 mmol of Ru(phen)Cl4 were added to a flask containing 10 mL of N,N-dimethylformamide (DMF). The reaction was carried out at 130 °C for 12 h under a nitrogen atmosphere. After cooling to room temperature, it was diluted with deionized water, filtered by suction, and the precipitate was washed with dimethyl sulfoxide (DMSO), water, and absolute ethanol respectively, and then dried in vacuo at 40 °C for 24 h to obtain the phenyl-linked ruthenium(II) homogeneous linear polymer material.

[0085] Example 5

[0086] 1 mmol of bipbz prepared in Example 1 and 1.15 mmol of Ru(phen)Cl4 were added to a flask containing 50 mL of N,N-dimethylacetamide (DMAC). The reaction was carried out at 140 °C for 3 h under a nitrogen atmosphere. After cooling to room temperature, it was diluted with deionized water, filtered by suction, and the precipitate was washed with dimethyl sulfoxide (DMSO), water, and absolute ethanol respectively, and then dried in vacuo at 40 °C for 24 h to obtain the phenyl-linked ruthenium(II) homogeneous linear polymer material.

[0087] Example 6

[0088] 1 mmol of bipbz prepared in Example 1 and 1.1 mmol of Ru(phen)Cl4 were added to a flask containing 15 mL of N,N-dimethylformamide (DMF) and 15 mL of N,N-dimethylacetamide (DMAC). The reaction was carried out at 150 °C for 24 h under a nitrogen atmosphere. After cooling to room temperature, it was diluted with deionized water, filtered by suction, and the precipitate was washed with dimethyl sulfoxide (DMSO), water, and absolute ethanol respectively, and then dried in vacuo at 40 °C for 24 h to obtain the phenyl-linked ruthenium(II) homogeneous linear polymer material.

[0089] Comparative Example 1 Binuclear Complex

[0090] 1 mmol of bipbz prepared in Example 1 and 2 mmol of Ru(phen)2Cl2 were added to a flask containing 30 mL of ethylene glycol. Under a nitrogen atmosphere, it was refluxed at 120 °C for 8 h; after cooling to room temperature, it was diluted with deionized water, and a saturated ammonium hexafluorophosphate solution was added to completely precipitate the precipitate. It was filtered by suction and the precipitate was washed thoroughly with deionized water, and then dried in vacuo at 40 °C for 24 h; to obtain the binuclear complex Ru-phen-bipbz-2; yield: 1.34 g, yield rate: 85%; the structure is:

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

[0092] Structure characterization:

[0093] 1. MALDI-TOF analysis was performed on Ru-phen-bipbz-n prepared in the example. The MALDI-TOF-MS spectrum in the range of 200 to 2000 Da is as shown in Figure 4 ; the MALDI-TOF-MS spectrum in the range of 2 kDa to 10 kDa is as shown in Figure 5 .

[0094] Due to the poor solubility of the Ru-phen-bipbz-n polymer material, MALDI-TOF-MS was used to characterize its molecular weight. Judging from the results of the MALDI-TOF-MS spectrum Figure 4 in the range of 200 to 2000 Da, obvious fragment peak fragments exist in Ru-phen-bipbz-n. These fragment peaks are highly similar to the MALDI-TOF test results of their corresponding binuclear complexes (Comparative Example 1) under the same experimental conditions. At the same time, the peak attribution can also be identified by simulating the peaks of this part.

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

[0096] When analyzing the high molecular weight region of Ru-phen-bipbz-n in the range of 2 kDa to 10 kDa, some significant peaks were observed, corresponding to peaks of different degrees of polymerization, which were: 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 indicate that polymers with different degrees of polymerization can be detected, and at the same time, they also indicate that the final product is a multi-component polymer containing different degrees of polymerization.

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

[0098] Elements C, O, N, and Ru can be detected in Ru-phen-bipbz-n, indicating that the material preparation was successful; the narrow spectrum shows that the peaks of C1s and N1s of the polymer shifted towards higher binding energies. This may be because the linear polymer of ruthenium (II) can continuously extend the chain lengths at both ends of the organic ligand. During the polymerization process, the content ratio of the auxiliary ligand phenanthroline (phen) with a lower binding energy of its own will decrease as the chain length increases, ultimately resulting in the binding energy of the Ru(II) linear polymer material shifting towards a higher binding energy.

[0099] 3. XRD tests were carried out on the Ru-phen-bipbz-n prepared in the examples, and the results are as Figure 7 shown.

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

[0101] 4. The microscopic morphology of the Ru-phen-bipbz-n prepared in the example was tested. The SEM image is as shown in Figure 8 the left figure; the TEM image is as shown in Figure 8 the right figure; the EDS image is as shown in Figure 9 the figure.

[0102] Ru-phen-bipbz-n presents a compact layered crystal structure, with small sizes and overall uniform distribution, indicating its good crystallinity and more uniform morphology. The TEM image further shows the layered stacked morphological structure of Ru-phen-bipbz-n, indicating that the sample has a high degree of order and good crystallinity. The EDS elemental 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 binding of the organic ligand to the metal center.

[0103] 5. The thermal stability analysis of the Ru-phen-bipbz-n prepared in the example was carried out. The test results of thermogravimetric analysis (TGA) are as shown in Figure 10 the figure.

[0104] The mass loss of Ru-phen-bipbz-n is only 4.42% at 300 °C and 34.59% at 800 °C. These results indicate that the Ru-phen-bipbz-n material exhibits good thermal stability, indicating that the coordination bond between the Ru(II) center and the ligand is relatively stable and can maintain the stability of the framework structure at higher temperatures.

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

[0106] 6. The ultraviolet absorption analysis of the Ru-phen-bipbz-n prepared in the example and the Ru-phen-bipbz-2 prepared in Comparative Example 1 was carried out. The UV-Vis absorption spectra of 20 μg / mL of Ru-phen-bipbz-n and Ru-phen-bipbz-2 were tested in dichloromethane, ethanol, water, acetonitrile, and acetone respectively; the results are as shown in Figure 11As shown, where a is Ru-phen-bipbz-2 and b is Ru-phen-bipbz-n. The solid UV-Vis-NIR test was carried out on Ru-phen-bipbz-n, and the spectrogram is as Figure 12 shown.

[0107] The results show that both the binuclear complex of Comparative Example 1 and the linear polymer of the Example 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 ruthenium(II) linear polymer. During the polymerization process, as the polymer chain length increases, the content of the ligand phen gradually decreases. Therefore, the absorption band at 275 nm generated by the π-π* transition caused by 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, this further promotes the charge transfer of the ligand itself, resulting in an enhanced absorption band at 360 nm. In addition, the absorption band at 460 nm generated by the MLCT transition also becomes weaker due to the decrease in the ratio of phen to the metal center, causing the absorption peak of the linear polymer at this wavelength to be lower than its corresponding binuclear complex. The results of the solid ultraviolet-visible-near-infrared light absorption test on Ru-phen-bipbz-n show that the polymeric material has effective absorption in the near-infrared spectral range, indicating its potential application in the optical properties in the near-infrared region.

[0108] Example 7

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

[0110] Comparative Example 2

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

[0112] Performance test:

[0113] 1. Photothermal conversion ability test

[0114] The Ru-phen-bipbz-n prepared in the example and 2 parts of the Ru-phen-bipbz prepared in Comparative Example 1 were tested under 808 nm laser irradiation with different power densities. The change in the highest surface temperature of the Ru-phen-bipn-n powder is as Figure 13 shown; a cyclic photothermal experiment was carried out under a power density of 1 W / cm 2 . The change in the highest surface temperature of the Ru-phen-bipn-n powder is as Figure 14 shown; a real-time infrared thermal imager picture of the effect of one photothermal cycle is as Figure 15 shown.

[0115] Under 808 nm laser irradiation, the surface temperature of the polymer powder sample rises rapidly within 5 seconds. After the laser is turned off, the temperature of the sample quickly returns to room temperature within 10 seconds. As the laser power density increases, the highest temperature that the material surface can reach increases accordingly, showing an obvious positive correlation with the laser power density. Under the irradiation of an 808 nm laser with a power density of 2 W / cm 2 , the highest surface temperature of the Ru-phen-bipbz-n powder reached 335.7 °C.

[0116] To further test the stability of the photothermal conversion of the material, the samples were respectively subjected to cyclic photothermal experiments under a power density of 1 W / cm 2 . After five cycles of testing, Ru-phen-bipbz-n still maintained a stable and rapid photothermal response. At the same time, its photothermal performance was hardly lost. During the long-term laser irradiation process, no obvious photo-bleaching phenomenon occurred in the sample, which further verified its excellent photothermal stability. The above experimental results show that these materials have good photothermal conversion efficiency and stability and can be well applied in the fields of energy conversion and storage, etc.

[0117] 2. Water evaporation capacity test

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

[0119] The contact angles of the photothermal material layer of the Janus evaporator loaded with Ru-phen-bipbz-n were 104.8° ( Figure 16), while the bottom end maintains the hydrophilicity of MFS, which conforms to the design concept of a Janus evaporator with a hydrophobic top and a hydrophilic bottom. While ensuring the efficient transport of water from the bottom layer to the layer containing the photothermal material for water evaporation, it also enhances the overall heat dissipation performance of the evaporator. The Janus evaporator was placed under an 808 nm laser for testing of its photothermal conversion performance. The results showed that under 808 nm laser irradiation, when the power density was 1 W / cm 2 , the surface temperature of the Janus evaporator responded rapidly within 10 seconds and reached a steady state within 60 seconds, and the results met our design expectations. Among them, the temperature of Ru-phen-bipbz-n was 163.4 °C. In contrast, the surface temperature of pure MFS was only 26.4 °C( Figure 17 ). This indicates that the Janus evaporator prepared in this application has the ability of more rapid response and more efficient photothermal conversion under 808 nm laser irradiation.

[0120] The bottom end of the evaporator was immersed in water and the photothermal material layer was irradiated with an 808 nm laser, and at the same time, the mass loss of water and the corresponding evaporation rate were recorded. The change of water evaporation amount with time is as shown in Figure 18 a; the change of evaporation rate with irradiation time is as shown in Figure 18 b.

[0121] As shown in Figure 18 , the water evaporation amount of pure MFS under 808 nm laser irradiation was only 0.25 kg·m -2 , and the evaporation efficiency was 0.50 kg·m -2 ·h -1 . In contrast, the Janus evaporator loaded with the photothermal material Ru-phen-bipbz-n showed a higher water evaporation amount and evaporation rate. The water evaporation amount was 0.81 kg·m -2 , and the evaporation efficiency was 1.63 kg·m -2 ·h -1 , and the improvement in evaporation performance compared to pure MFS was 228%, and this improvement is a very remarkable result.

[0122] To evaluate the anti-salt precipitation performance of the Janus evaporator under high water evaporation, the effects of NaCl solutions with different mass concentrations (0%, 5.0%, 10.0%, 15.0% wt%) on the evaporation performance of the Janus evaporator were evaluated. The change of water evaporation amount of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations with time is as shown in Figure 19 a; the change of evaporation rate of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations with irradiation time is as shown in Figure 19As shown in b; the desalination rates of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations are as Figure 20 shown in a; the desalination rates and evaporation rates of the Janus evaporator loaded with Ru-phen-bipbz at different NaCl concentrations are as Figure 20 shown in b.

[0123] From Figure 19 it can be known that when the Janus evaporator loaded with Ru-phen-bipbz-n evaporates a 5% NaCl solution, the water evaporation amount is 0.69 kg·m -2 , and the evaporation efficiency is 1.3832 ± 0.02346 kg·m -2 ·h -1 , when evaporating a 15% NaCl solution, the water evaporation amount is 0.51 kg·m -2 , and the evaporation efficiency is 1.0175 ± 0.03887 kg·m -2 ·h -1 . It can be seen from the above test data that when the Janus evaporator loaded with Ru-phen-bipbz-n is in NaCl solutions with different mass concentration gradients, it shows a trend that the evaporation performance decreases with the increase of the solution concentration. We speculate that such a result may be due to the partial adsorption of NaCl crystals inside the Janus evaporator during the evaporation process, which hinders the transportation of water.

[0124] Even so, the test results of the above Janus evaporator in evaporating a 15% NaCl solution are significantly better than the evaporation performance of pure MFS. In addition, from Figure 20 it can be known that the desalination rates for NaCl solutions with different mass concentrations all exceed 99.5%. It should be noted that no salt crystal crystallization phenomenon was observed during the whole experiment process. These results indicate that the prepared Janus evaporator can show excellent water evaporation performance and excellent salt resistance even under high salinity conditions, highlighting its potential in the field of efficient seawater desalination applications.

[0125] 3. Water quality purification ability test

[0126] The Janus evaporator prepared in Example 7 was used to conduct a simulation experiment on the actual seawater desalination process. The experimental results show that the concentrations of the four main ions (Na + , Mg 2+ , Ca 2+ , K + ) in the seawater sample collected from the East China Sea are all reduced to below 1 ppm in the condensate water after evaporation, significantly lower than the 10 - 500 ppm that can be achieved by the traditional membrane-based reverse osmosis method ( Figure 21 a). In addition, the Ru in the water sample before and after evaporation2+ No obvious change in concentration was detected, indicating that the introduction of the photothermal material would not cause loss of photothermal resources. At the same time, Ru 2+ would not leak through the Janus evaporator, thus avoiding potential hazards 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 for water evaporation, the condensed water was collected during the evaporation process, and ultraviolet-visible absorption spectroscopy was used for analysis. The results are as Figure 21 shown; where b is CR; c is MO; d is MB.

[0128] Figure 21 It was 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 samples, indicating that these organic pollutants did not appear in the purified water during the evaporation process.

[0129] In summary, the organic ligand of the structure shown in Formula I of this application constructs a homogeneous linear polymer with ruthenium(II) metal, while retaining the excellent optical properties of the ruthenium(II) metal complex and combining the structural advantages of the supramolecular MOFs material, enabling the polymer to achieve efficient applications in the fields of photothermal conversion, water evaporation and water purification.

[0130] The above embodiments are only the preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A phenylene-linked ruthenium(II) homogeneous linear polymer material, characterized in that, In the organic ligand with the structure shown in Formula I, two nitrogen atoms on the same phenanthroline coordinate with the same ruthenium atom, and one phenanthroline on two adjacent organic ligands with the structure shown in Formula I coordinates with one ruthenium atom respectively.

2. A preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer material, characterized in that 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 phenylenediyl-linked ruthenium(II) homogeneous linear polymer material.

3. The preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to claim 2, characterized in that the molar ratio of the organic ligand with the structure shown in Formula I to Ru(phen)Cl4 is 1:(1 - 1.2).

4. The preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to claim 2, 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.

5. The preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to claim 2, characterized in that the inert gas atmosphere is a nitrogen or argon atmosphere; the reaction conditions are to react at 120 - 150 °C for 3 - 24 h.

6. The preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer 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 absolute ethanol respectively, and vacuum dried at 35 - 50 °C.

7. The preparation method of a phenylenediyl-linked ruthenium(II) homogeneous linear polymer 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-benzenedicarboxaldehyde in the presence of an ammonium salt.

8. Application of the phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to claim 1, and the phenylenediyl-linked ruthenium(II) homogeneous linear polymer material prepared by the preparation method of the phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to any one of claims 2 - 7 as a photothermal conversion material.

9. The application according to claim 8, wherein The phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to claim 1, or the phenylenediyl-linked ruthenium(II) homogeneous linear polymer material prepared by the preparation method of the phenylenediyl-linked ruthenium(II) homogeneous linear polymer material according to any one of claims 2 - 7 is used as a photothermal conversion material for seawater desalination and wastewater purification.

10. An evaporator, characterized in that, The evaporator is a Janus evaporator, and the evaporator comprises a phenyl-linked ruthenium(II) homogeneous linear polymer material as described in claim 1 or a phenyl-linked ruthenium(II) homogeneous linear polymer material prepared by the preparation method of the phenyl-linked ruthenium(II) homogeneous linear polymer material according to any one of claims 2-8.

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