CN114105906B - Organic charge transfer eutectic crystal and preparation method and application thereof - Google Patents
Organic charge transfer eutectic crystal and preparation method and application thereof Download PDFInfo
- Publication number
- CN114105906B CN114105906B CN202111327887.1A CN202111327887A CN114105906B CN 114105906 B CN114105906 B CN 114105906B CN 202111327887 A CN202111327887 A CN 202111327887A CN 114105906 B CN114105906 B CN 114105906B
- Authority
- CN
- China
- Prior art keywords
- charge transfer
- organic charge
- eutectic
- abts
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/006—Methods of steam generation characterised by form of heating method using solar heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S20/00—Solar heat collectors specially adapted for particular uses or environments
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Polymers & Plastics (AREA)
- Combustion & Propulsion (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic charge transfer eutectics, and particularly relates to an organic charge transfer eutectic based on a persistent cation free radical acceptor and a preparation method and application thereof. An organic charge transfer eutectic crystal is prepared from TMB and ABTS +· The compound reacts with water molecules to form a one-dimensional organic charge transfer eutectic crystal; the absorption spectrum of the organic charge transfer eutectic is 300-2500nm; the ABTS +· The structural formula of (A) is:
the structural formula of the TMB is
Description
Technical Field
The invention belongs to the field of organic charge transfer eutectics, and particularly relates to an organic charge transfer eutectic based on a persistent cation free radical acceptor and a preparation method and application thereof.
Background
Solar energy, as a clean renewable energy source, is huge in energy, is not limited by conditions of exploitation, transportation and storage, and has been widely applied to solar photovoltaic and solar photothermal. The solar photovoltaic is that the photovoltaic effect of a semiconductor interface is utilized to directly convert light energy into electric energy; the solar photo-thermal method is to convert light energy into heat energy by using a solar absorber. Solar optothermal has higher conversion efficiency than solar photovoltaics because it can utilize a wider bandwidth within the solar spectrum (almost the entire solar spectrum). In recent years, solar photo-thermal technology has attracted much attention in the fields of seawater desalination and water treatment due to high efficiency of interface photo-thermal conversion efficiency. In this system, an ideal solar absorber should have the advantages of efficient broad-spectrum solar absorption, high efficiency of photothermal conversion, and good stability. Solar absorber materials developed at present are mainly focused on multilayer thin film coatings, carbon-based and plasma-based inorganic materials. Although they can achieve high solar heat conversion performance through reasonable design, the disadvantages of high cost and thermal instability limit the practical application of the solar heat conversion performance. Therefore, it is a challenge to develop a solar absorber material with a broad absorption spectrum, low cost, high solar-to-thermal conversion efficiency and good stability.
Organic charge transfer co-crystals are a class of single crystal materials composed of a donor (D) and an acceptor (a) in a stoichiometric ratio through charge transfer interactions. The charge transfer eutectic engineering benefits from the cooperative strategy of different components and has the advantages of flexible structure, solution-soluble treatment, low cost and the like, and becomes an effective and universal method for constructing functional materials, particularly organic photoelectric materials. Among them, charge transfer eutectic engineering is an effective way to prepare organic photothermal materials because efficient charge transfer between donor and acceptor can generate charge transfer complexes with narrower band gaps than the original components. In recent years, the successive development of several near-infrared photothermal co-crystals greatly expands the potential application of organic small molecular materials in the field of solar heat conversion. Unfortunately, mismatches in structure or electron clouds in the D-a complex often lead to failure of the charge transfer process. On the other hand, photo-thermal charge transfer co-crystals with full spectrum absorption are less formed due to weaker charge transfer interactions. Therefore, the development of stable and full spectrum absorption organic charge transfer co-crystals is of great significance and challenging for efficient solar thermal energy conversion.
Disclosure of Invention
The invention provides an organic charge transfer eutectic and a preparation method and application thereof, the preparation method is simple, the cost is low, the organic charge transfer eutectic can be produced in a large scale, and the prepared organic charge transfer eutectic has broad-spectrum absorption (300-2500 nm) and high-efficiency photo-thermal conversion. Polyurethane sponges doped with the organic charge transfer co-crystal showed excellent water evaporation rates (1.407 kg m) - 2 h -1 ) And high efficiency solar-to-steam conversion efficiency (97.0%).
In order to solve the technical problems, the technical scheme of the invention is as follows:
the first aspect of the invention provides an organic charge transfer eutectic which is prepared from TMB and ABTS +· The compound reacts with water molecules to form a one-dimensional organic charge transfer eutectic crystal; the absorption spectrum of the organic charge transfer eutectic is 300-2500nm;
the ABTS +· The structural formula of (A) is as follows:
the structural formula of the TMB is
Preferably, the TMB and ABTS +· The molar ratio of (a) to (b) is 0.5 to 1.
Preferably, the ABTS +· By ABTS 2- And (4) oxidizing to obtain the catalyst.
The second aspect of the present invention provides a method for preparing the organic charge transfer co-crystal, comprising the steps of:
1) Divalent negative 2,2' -biazoyl-bis-3-ethylbenzothiazoline-6-sulfonic Acid (ABTS) 2- ) Carrying out oxidation reaction on the catalytic action of nano enzyme and hydrogen peroxide in a weak acid environment, and centrifuging to obtain ABTS +· A solution;
2) Will ABTS +· Mixing the solution with 3,3', 5' -Tetramethylbenzidine (TMB) to obtain charge transfer complex, standing and precipitatingPrecipitating, freezing and drying to obtain the organic charge transfer eutectic;
the negatively divalent 2,2' -diaza-bis-3-ethylbenzothiazoline-6-sulfonic Acid (ABTS) 2- ) The structural formula of (A) is as follows:
preferably, the nanoenzyme is a peroxidase-like enzyme.
More preferably, the peroxidase-like enzyme is at least one selected from the group consisting of CoPt @ G, ru @ G and Pt @ G.
Selecting nanometer enzyme with peroxidase-like property such as Ru @ G for catalyzing ABTS 2- Oxidation to ABTS +· The unusual persistence of such radical cations is due to the distribution of an odd number of electrons over an even number of atoms, as shown by its resonant structure (as follows):
the obtained organic charge transfer eutectic has high absorption value in the range of 1000-1100nm, and narrow band gap and non-radiative decay promoted by pi-pi interaction, so that the eutectic can emit laser light (0.3W/cm) at 1064nm 2 ) Under irradiation, the photo-thermal conversion efficiency can reach 49.6%.
Preferably, the concentration of the nano enzyme is 0.05-0.2 mug/mL.
ABTS generated by too low concentration of nano-enzyme +· The yield is low, and if the yield is too large, waste is caused.
Preferably, in step 1), ABTS 2- The concentration of (B) is 0.1 to 2mM.
ABTS 2- Is rich inSpending small generating ABTS +· The yield of (2) is low, and when the yield is too large, waste is generated, and the trouble of purification is increased.
Preferably, in step 1), the final concentration of hydrogen peroxide is 5-20mM;
also, ABTS produced with too small a concentration of hydrogen peroxide +· The yield is low, and if the yield is too large, waste is caused.
Preferably, in step 1), the pH of the weakly acidic environment is 3 to 6.
Preferably, in step 1), the weakly acidic environment is achieved by adding an acidic solution.
Preferably, the acidic solution includes at least one of a phosphate buffer, a carbonate buffer, an acetate buffer, or a hydrochloric acid solution.
Preferably, in step 1), the oxidation reaction temperature is 4 to 40 ℃.
Preferably, in the step 1), the rotation speed of the centrifugation is 8000-12000 rpm.
Preferably, the step 2) also comprises dissolving TMB into organic solvent in advance, and then mixing with ABTS +· And (4) reacting the solution.
Preferably, the organic solvent is selected from at least one of ethanol, acetonitrile and dimethyl sulfoxide.
TMB is poorly soluble in water and the organic solvent serves to dissolve the TMB, thereby allowing the reactants to form a homogeneous co-solvent.
Preferably, in the step 2), the standing and precipitating time is 6-24 h.
The third aspect of the invention provides a preparation method of polyurethane sponge doped with organic charge transfer eutectic, which comprises the following steps:
and mixing the organic charge transfer eutectic with polyurethane A glue and polyurethane B glue, quickly stirring, and standing for foaming to obtain the polyurethane sponge doped with the organic charge transfer eutectic.
The polyurethane sponge is also called polyurethane foaming heat-insulating material and consists of isocyanate (A glue) and combined polyether (B glue)
Preferably, the mass ratio of the eutectic powder to the polyurethane sponge is 0.01-0.03: 1.
preferably, the mass ratio of the polyurethane A glue to the polyurethane B glue is 1.2-1.8: 1.
preferably, the foaming temperature is 20-40 ℃.
The invention provides polyurethane sponge doped with organic charge transfer eutectic, and the polyurethane sponge is obtained by the preparation method.
The fifth aspect of the invention provides an application of the polyurethane sponge doped with the organic charge transfer eutectic, wherein the polyurethane sponge doped with the organic charge transfer eutectic is used for a solar interface evaporator; the solar interface evaporator can be used for instant power and fresh water production.
Compared with the prior art, the invention has at least one of the following beneficial effects:
a) The preparation method is simple, low in cost and suitable for large-scale production.
b) The organic charge transfer eutectic disclosed by the invention has full solar spectrum absorption, good stability and excellent NIR-II photothermal conversion efficiency which is as high as 49.6%, and is very considerable in organic photothermal materials.
c) The invention selects a specific lasting cation free radical as a charge transfer receptor to form a stable organic charge transfer eutectic with TMB; the method is not reported in the prior charge transfer eutectic, enriches the types of charge transfer acceptors, and also widens the application of organic free radicals in functional materials.
d) The invention selects porous polyurethane with low heat conductivity coefficient as a frame material, is beneficial to realizing interface solar heat conversion, efficiently utilizes heat energy to realize evaporation of water molecules, and has wide application prospect in the aspect of solar-driven seawater desalination.
Drawings
FIG. 1 shows ABTS in example 1 +· A characterization map of (a); wherein a) is ABTS +· Ultraviolet-visible-near infrared absorption spectrum of (a); b) As ABTS +· Electron paramagnetic resonance spectroscopy of (1);
fig. 2 is a structural analysis diagram of an organic charge transfer eutectic TAHC in example 2; wherein, a) is a scanning electron micrograph of TAHC; b) Is a transmission electron micrograph of TAHC; c) Selected area electron diffraction patterns for TAHC; d) Powder X-ray diffraction spectra for TAHC and TMB; e) Is a crystal structure analytic diagram of TAHC;
FIG. 3 is a graph showing the characterization of the organic charge transfer eutectic TAHC in example 3; wherein, a) is the theoretically calculated HOMO-LUMO energy level; b) Is the ultraviolet-visible-near infrared absorption spectrum of TAHC;
FIG. 4 is a UV-VIS-NIR absorption spectrum of the organic charge transfer eutectic TTC of example 4;
FIG. 5 is a graph showing the photothermal conversion performance of the organic charge transfer eutectic in example 5 under a 1064nm laser; wherein a) is a photothermal temperature rise curve of the TAHC powder; b) The temperature rise and reduction curve of the TAHC powder under different laser powers is shown; c) A circulating temperature rising and reducing curve of the TAHC powder is obtained; d) A photothermographic image of the TAHC powder;
FIG. 6 is a graph of solar driven water evaporation of polyurethane sponge doped with organic charge transfer co-crystals of example 6; wherein a) is the ultraviolet-visible-near infrared absorption spectrum of PU-TAHC; b) A temperature rise curve of PU-TAHC under the irradiation of the sunlight simulator; c) A temperature rise curve of PU-TAHC floating on the water surface is shown; d) Is a graph of the solar driven water evaporation rate of PU-TAHC.
Detailed description of the preferred embodiments
The embodiments of the present invention will be described with reference to examples
Example 1
ABTS +· The preparation method of the solution comprises the following steps:
diluting the hydrochloric acid aqueous solution to obtain a weak acid solution with pH 4; using water as solvent to prepare 50mM of negative bivalent 2,2' -biazo-bi-3-ethyl benzothiazole-6-sulfonic Acid (ABTS) 2- ) Storing the solution at 4 ℃; ru @ G nanoparticles were diluted to 0.1. Mu.g/mL. 39.5mL of diluted aqueous hydrochloric acid solution having pH 4 was added to a 50mL centrifuge tube, and 300. Mu.L of 50mM ABTS was added 2- Solution, 200. Mu.L 1M H 2 O 2 40 μ L of 100 μ g/mL Ru @ G, shaking uniformly, and gradually changing the solution from colorless to green to obtain Ru @ G and ABTS +· Green mixed solution; standing for 12h, and collecting ABTS by centrifugation +· Green solution, ionThe core rotation speed was 10000rpm. For ABTS +· The characterization was performed, and the results are shown in fig. 1; wherein a) is ABTS +· Ultraviolet-visible-near infrared absorption spectrum of (a); b) Is ABTS +· Electron paramagnetic resonance spectroscopy. As can be seen, the ABTS obtained +· The results show that ABTS can be proved by the characteristic peak of the ultraviolet-visible-near infrared absorption spectrum of the solution at 734nm and the strong signal of the ESR spectrum of the solution, which indicates the existence of unpaired electrons +· The successful preparation.
Example 2
The preparation method of the organic charge transfer eutectic based on the persistent cationic free radicals comprises the following steps:
all ABTS collected in example 1 +· The solution was added to a 20mL serum bottle, and then 2mL of 10mM TMB mother liquor, in which TMB was dissolved in ethanol, was added. The color is rapidly changed from green to blue and gradually generates flocculent, finally, a large amount of blue-green eutectic is precipitated at the bottom of the bottle, crystals are collected, and then the crystals are cooled, freeze-dried and dried to obtain the organic charge transfer eutectic TAHC powder.
Performing structural analysis on the organic charge transfer eutectic TAHC, wherein a) is a scanning electron micrograph of the TAHC, as shown in FIG. 2; b) Transmission electron micrograph of TAHC; c) Selected area electron diffraction for TAHC; d) Powder X-ray diffraction spectra for TAHC and TMB; e) An analytical diagram of the crystal structure of TAHC. Therefore, the prepared eutectic crystal is in a 1-dimensional long straight rod shape, and the section of the eutectic crystal is quadrilateral. The eutectic is along [010 ] as can be seen by combining transmission electron microscopy and selected area electron diffraction patterns]And (4) growing in a direction. The powder X-ray diffraction spectrum shows that the TAHC and donor TMB are different crystals, and the sharp peak proves that the crystallinity of the TAHC is good. The HOMO-LUMO energy level of the organic charge transfer eutectic TAHC was theoretically calculated as shown in fig. 3. The results (a in FIG. 3) show that the HOMO level (-5.71 eV) of TAHC is closer to that of TMB (-4.93 eV), and the LUMO level (-4.86 eV) of TAHC is closer to that of ABTS +· The LUMO energy level (-4.26 eV) further illustrates the electron transfer from TMB to ABTS, resulting in a narrow bandgap of 0.31 eV. By combining with ultraviolet-visible-near infrared absorption spectrogram of organic charge transfer eutectic TAHC, the visible TAHC shows wide absorption on the ultraviolet-visible-near infrared absorption spectrum, which exceeds 2500nm (b in fig. 3). This result is closely related to the HOMO-LUMO energy level. This is broader than the absorption range (300-1600 nm) reported in the literature for charge transfer complexes formed with the same donor TMB and acceptor F4TCNQ, further demonstrating ABTS +· The contribution made therein.
Example 3
The preparation method of the organic charge transfer co-crystal based on the common acceptor is the same as that in example 2, except that the influence of different types of acceptors on the absorption performance of the charge transfer co-crystal is compared.
ABTS of example 2 +· The solution is changed into a 1,2,4, 5-Tetracyanobenzene (TCNB) solution, and the mass ratio of TMB to TCNB is 1:1; a TMB-TCNB charge transfer co-crystal (TTC) was obtained as a control for the cationic radical acceptor.
Ultraviolet-visible-near infrared absorption spectrum tests are carried out on the TMB-TCNB charge transfer eutectic, and the experimental results (figure 4) show that the absorption of the TTC eutectic can only reach 1000nm. It is well established that the type of acceptor can have a great influence on the nature of the charge transfer formed, in particular on the uv-vis-nir absorption, and thus on their photothermal properties, with the same donor.
Example 4
The organic charge transfer eutectic TAHC prepared in example 2 was subjected to a photothermal conversion performance graph test, and the results are shown in fig. 5, in which a) in fig. 5 is a photothermal temperature increase curve of the TAHC powder; b) A temperature rise and drop curve of the TAHC powder under different laser powers is obtained; c) A circulating temperature rising and reducing curve of the TAHC powder is obtained; d) The photo-thermal imaging graph of the TAHC powder has excellent near-infrared two-region photo-thermal conversion effect. As shown in a in FIG. 5, TAHC powder was irradiated with 1064nm laser (0.5W/cm) 2 ) The temperature rapidly increased from room temperature to 85 ℃ while the blank (i.e., quartz glass on which TAHC powder was spread for laser irradiation) had little change in temperature. And the TAHC powder has better effect of rapid temperature rise under the laser irradiation of 300-2500 nm. Meanwhile, the temperature raising ability of TAHC is also closely related to the laser power (b in fig. 5), and the higher the laser power is, the stronger the temperature raising ability is. We examine the photo-thermal stability of TAHC, and five-round photo-thermal cycle results show that TAHC has excellent performanceDifferential photothermal stability (c in fig. 5). Finally, the photothermographic performance of TAHC was examined (d in fig. 5), and the image pattern became brighter with increasing irradiation time, and in particular, the imaging effect was shown at the 1 st s of irradiation, demonstrating that TAHC is an excellent near-infrared photothermographic material. Due to the very low absorption of TTC at 1064nm, the photothermal properties of TTC under 1064nm laser irradiation are almost negligible. The photo-thermal conversion efficiency of TAHC under 1064nm laser irradiation is 49.6%, which is higher than that of the TMB-F4TCNQ compound (48.0%), the TMB-TCNQ compound (42.4%), the DBTTF-TCNB eutectic (18.8%) and the TTF-Tri-PMDI eutectic (15.0%) reported in the prior art.
Example 6
The preparation method of the polyurethane sponge doped with the organic charge transfer eutectic comprises the following steps:
adding 30mg of TAHC powder collected in example 3 into a customized polytetrafluoroethylene mold, adding 0.6g of polyurethane A glue and 0.4g of polyurethane B glue, wherein the polyurethane A glue and the polyurethane B glue are s-12 purchased from Guangan chemical company Limited, rapidly stirring to be uniform by using a handheld tissue grinding instrument, waiting for mixed glue to foam at room temperature, and taking the prepared eutectic-doped polyurethane sponge (PU-TAHC) out of the mold after foaming is complete to obtain a regular shape. Similarly, a blank polyurethane sponge (PU) was prepared as a control without the addition of TAHC powder. Two sponges were tested, as shown in fig. 6, where a) is the uv-vis-nir absorption spectrum of PU-TAHC; b) A temperature rise curve of PU-TAHC under the irradiation of the sunlight simulator; c) A temperature rise curve of PU-TAHC floating on the water surface is shown; d) Is a graph of the solar driven water evaporation rate of PU-TAHC. As shown in FIG. 6 a, PU-TAHC has broad absorption (300-2500 nm), including almost the entire solar spectrum. The molecular weight is higher than that of the TMB-F4TCNQ compound and the TMB-TCNQ compound which are reported in the prior art, and the molecular weight is 300-1600 nm. Under the irradiation of a solar simulator (1 kW/m) 2 ) The surface temperature of PU-TAHC rapidly increased from room temperature to 95.6 deg.C, whereas PU was able to rise only to 39 deg.C (b in FIG. 6). The PU-TAHC floats on the water surface, under the irradiation of a sunlight simulator, the light can be converted into heat to be focused on the PU-TAHC, the temperature is quickly increased to 47.4 ℃ from 23.5 ℃,while the PU temperature slowly rises slightly (c in FIG. 6). Correspondingly, the water evaporation rate of PU-TAHC can reach 1.407kg/m 2 h, the evaporation rates of PU and pure water are similar, and the evaporation rates of PU and pure water can only reach 0.511kg/m respectively under the same irradiation condition 2 h and 0.462kg/m 2 h (d in fig. 6), further demonstrating the greater feasibility of TAHC in interfacial solar-driven water evaporation systems. The solar energy conversion efficiency of the PU-TAHC is obtained by calculation and reaches 97.0 percent. Under the same conditions, the water evaporation rate of the CTCC-S is 1.67kg/m 2 h, and a solar conversion efficiency of 90.3%, indicating that the charge transfer co-crystal of the present invention based on persistent cationic radical acceptors is more advantageous in solar driven water evaporation systems.
Claims (13)
1. An organic charge transfer eutectic crystal is characterized in that the organic charge transfer eutectic crystal is prepared from TMB and ABTS +· The compound reacts with water molecules to form a one-dimensional organic charge transfer eutectic crystal; the absorption spectrum of the organic charge transfer eutectic is 300-2500nm;
the ABTS +· The structural formula of (A) is as follows:
the structural formula of the TMB is
2. The organic charge transfer co-crystal of claim 1, wherein TMB and ABTS are +· The molar ratio of (A) to (B) is 0.5-1: 1.
3. Method for the preparation of an organic charge transfer co-crystal according to any of claims 1 to 2, characterized in that it comprises the following steps:
1) Negetive divalent 2,2' -biazo-bis-3-ethylbenzothiaThe oxazoline-6-sulfonic acid is subjected to oxidation reaction under the catalytic action of nano enzyme and hydrogen peroxide in a weak acid environment, and is centrifuged to obtain ABTS +· A solution;
2) Will ABTS +· Mixing the solution with 3,3', 5' -tetramethyl benzidine to obtain a charge transfer compound, standing for precipitation, and freeze-drying to obtain the organic charge transfer eutectic;
the divalent negative 2,2' -biazo-bis-3-ethylbenzothiazoline-6-sulfonic Acid (ABTS) 2- ) The structural formula of (A) is as follows:
4. the method of preparing an organic charge transfer co-crystal of claim 3, wherein the nanoenzyme is a peroxidase-like enzyme.
5. The method of claim 4, wherein the peroxidase-like enzyme is at least one selected from CoPt @ G, ru @ G, and Pt @ G.
6. The method of preparing an organic charge transfer co-crystal of claim 4, wherein the concentration of nanoenzyme is 0.05-0.2ug/mL.
7. The method for preparing an organic charge transfer co-crystal according to claim 3, wherein in step 1), ABTS is used 2- The concentration of (A) is 0.1 to 2mM; in step 1), the final concentration of hydrogen peroxide is 5-20mM.
8. The method for preparing an organic charge transfer co-crystal according to claim 3, wherein the step 2) further comprises dissolving TMB in an organic solvent in advance, and then mixing with ABTS +· And (4) reacting the solution.
9. The method of preparing an organic charge transfer co-crystal of claim 8, wherein the organic solvent is selected from at least one of ethanol, acetonitrile, and dimethyl sulfoxide.
10. A preparation method of polyurethane sponge doped with organic charge transfer eutectic is characterized by comprising the following steps: mixing the organic charge transfer eutectic as claimed in claim 1 or 2 with polyurethane A glue and polyurethane B glue, stirring rapidly, and standing for foaming to obtain polyurethane sponge doped with the organic charge transfer eutectic.
11. The method for preparing the polyurethane sponge doped with the organic charge transfer eutectic crystal as claimed in claim 10, wherein the mass ratio of the eutectic powder to the polyurethane sponge is 0.01-0.03: 1; the mass ratio of the polyurethane A glue to the polyurethane B glue is 1.2-1.8: 1.
12. Polyurethane sponge doped with organic charge transfer co-crystals, obtained by the process for the preparation of polyurethane sponge doped with organic charge transfer co-crystals according to claim 10 or 11.
13. Use of the organic charge transfer eutectic-doped polyurethane sponge according to claim 12, wherein said organic charge transfer eutectic-doped polyurethane sponge is used in a solar interface evaporator; the solar interface evaporator can be used for instant power and fresh water production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111327887.1A CN114105906B (en) | 2021-11-10 | 2021-11-10 | Organic charge transfer eutectic crystal and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111327887.1A CN114105906B (en) | 2021-11-10 | 2021-11-10 | Organic charge transfer eutectic crystal and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114105906A CN114105906A (en) | 2022-03-01 |
| CN114105906B true CN114105906B (en) | 2023-03-17 |
Family
ID=80378008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111327887.1A Active CN114105906B (en) | 2021-11-10 | 2021-11-10 | Organic charge transfer eutectic crystal and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114105906B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102460B (en) * | 2023-02-13 | 2023-09-15 | 天津大学 | Quaternary spectrum organic eutectic material based on tetracyano-terephthalquinone and application thereof in water evaporation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805227B (en) * | 2016-09-09 | 2020-02-18 | 中国科学院化学研究所 | Supermolecule ion material, preparation method thereof and application thereof in preparing humidity sensing device |
| CN113214269B (en) * | 2020-01-21 | 2022-02-25 | 青岛科技大学 | Photothermal material and preparation method and application thereof |
-
2021
- 2021-11-10 CN CN202111327887.1A patent/CN114105906B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114105906A (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265020B (en) | Method for preparing graphene quantum dot powder on large scale | |
| CN111606319B (en) | Carbon nano coil, preparation method and application thereof, and carbon nano belt | |
| Allahbakhsh | Nitrogen-doped graphene quantum dots hydrogels for highly efficient solar steam generation | |
| CN112409998B (en) | Photo-thermal conversion eutectic material containing N, N, N, N-tetramethyl-p-phenylenediamine and preparation method thereof | |
| Gebreegziabher et al. | Polyaniline–graphene quantum dots (PANI–GQDs) hybrid for plastic solar cell | |
| Shi et al. | Efficient bottom-up synthesis of graphene quantum dots at an atomically precise level | |
| WO2020024766A1 (en) | Heteroatom doped polymer nanosphere/carbon nanosphere and preparation method thereof | |
| CN114105906B (en) | Organic charge transfer eutectic crystal and preparation method and application thereof | |
| Kuchkaev et al. | Chemical functionalization of 2D black phosphorus toward its applications in energy devices and catalysis: a review | |
| Huang et al. | Microwave assisted hydrothermal way towards highly crystalized N-doped carbon quantum dots and their oxygen reduction performance | |
| CN114835944A (en) | Energy-consumption self-sufficient type efficient photothermal evaporation nano-particle porous membrane and preparation method and application thereof | |
| CN111244490A (en) | Bamboo-shaped hollow N-doped carbon nanotube and C3N4Nanosheet cross-linked composite material and preparation method and application thereof | |
| Wang et al. | Asymmetric solar evaporator with salt-resistance capability for freshwater and energy generation | |
| Gupta et al. | Highly efficient S‐g‐CN/Mo‐368 catalyst for synergistically NADH regeneration under solar light | |
| Li et al. | Realize larger grain size of CH3NH3PbI3 film with reduced non-radiative recombination for high performance perovskite solar cells via precursor colloidal size engineering | |
| Chen et al. | Stability study of low-cost carbon quantum dots nanofluids with saline water and their application investigation for the performance improvement of solar still | |
| CN113403068A (en) | Fused carbon dot, preparation method and application thereof | |
| Shen et al. | One-step synthesis of intrinsically functionalized fluorescent carbon nanoparticles by hydrothermal carbonization from different carbon sources | |
| CN111097475A (en) | Hydrogen peroxide modified graphite phase carbon nitride nanosheet and preparation method thereof | |
| Wang et al. | Promoting infrared light driven photocatalytic activity of W 18 O 49 nanorods by coupling polypyrrole | |
| CN114835163B (en) | Novel tungsten sulfide photo-thermal material for water purification and preparation and application thereof | |
| CN107098337B (en) | A kind of preparation method of water-dispersion type nitrogen-doped graphene quantum dot | |
| CN109908920A (en) | It is a kind of to prepare 1T@2H-MoS2The method of/Au nanometer sheet | |
| CN108793099A (en) | A kind of radial selenium nanotube and preparation method thereof | |
| CN113861496A (en) | Polyimide/carbon quantum dot/zinc sulfide quantum dot composite aerogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |