CN115125612B - Organic eutectic synthesis method with photoelectric response performance and application - Google Patents
Organic eutectic synthesis method with photoelectric response performance and application Download PDFInfo
- Publication number
- CN115125612B CN115125612B CN202210630502.7A CN202210630502A CN115125612B CN 115125612 B CN115125612 B CN 115125612B CN 202210630502 A CN202210630502 A CN 202210630502A CN 115125612 B CN115125612 B CN 115125612B
- Authority
- CN
- China
- Prior art keywords
- tcnq
- eutectic
- organic
- organic eutectic
- dcz
- 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
- 230000005496 eutectics Effects 0.000 title claims abstract description 72
- 230000004044 response Effects 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims abstract description 17
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims abstract description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 230000005684 electric field Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004020 luminiscence type Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000005092 sublimation method Methods 0.000 claims description 3
- 238000002288 cocrystallisation Methods 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 37
- 239000000463 material Substances 0.000 abstract description 14
- 150000003254 radicals Chemical class 0.000 abstract description 12
- 238000004458 analytical method Methods 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000075 oxide glass Substances 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 230000009878 intermolecular interaction Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- -1 cationic free radical Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001481789 Rupicapra Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses an organic eutectic synthesis method with photoelectric response performance and application thereof, and belongs to the technical field of material science. According to the invention, electron-deficient molecules 7, 8-tetracyano-terephthalquinone dimethane and electron-donating molecules carbazole, dibenzothiophene and dibenzofuran are respectively co-crystallized to synthesize three novel organic eutectic crystals, and the novel organic eutectic crystals have rich cation free radicals under dark conditions without external light excitation. Organic eutectic is coated on the surface of an indium tin oxide glass electrode to prepare an organic eutectic modified conductive glass electrode, and under the action of an electric field, an electron donor and an electron acceptor in the organic eutectic are effectively separated and transferred, and a generated intramolecular electron transfer state activates photocurrent response in an aqueous medium. The organic eutectic is coated on the surface of the glassy carbon electrode to prepare the organic eutectic modified glassy carbon electrode, and the organic eutectic modified glassy carbon electrode has high-efficiency cathode electrochemiluminescence performance under the condition of no need of adding a co-reactant, and is expected to be used in the fields of semiconductor materials, photoelectric devices, environment detection, biological analysis and the like.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to an organic eutectic synthesis method with photoelectric response performance and application thereof.
Background
The photoelectric response is a phenomenon in which a substance collects photoelectrons under light irradiation to form an electric current (poddorska, a.; sushecki, m.; mech, k.et al light intensity-induced photocurrent switching effect. Nat. Commun.2020,11,854). The photoelectric functional material can effectively establish the connection between optics and electronics, and can reveal the head angle in various fields such as detection sensing, organic light emitting diodes, information processing and the like. The traditional photoelectric functional material mainly comprises two major types of inorganic photoelectric materials and organic photoelectric materials according to the composition. Inorganic photoelectric materials typified by silicon, titanium dioxide, and the like are widely used because of simple synthesis procedures, but their general properties are not stable enough to be used for a long period of time in practical applications (Teng, f.; hu, k.; ouyang, w.et al photoelectric detectors based on inorganic p-type semiconductor materials.adv.mate.2018, 30,1706262). The disadvantages of complicated synthesis steps, disordered structure, low photoelectric conversion efficiency and the like of organic photoelectric materials represented by phthalocyanine and porphyrin derivatives also greatly limit the application of the organic photoelectric materials (Ostroverkhova, O.organic optoelectronic materials: organs and applications. Chem. Rev.2016,116, 13279-13412).
In conventional chemical reactions, cleavage and formation of chemical bonds between atoms or molecules plays a key role in the synthesis of new compounds. Unlike traditional chemical synthesis, the organic eutectic structure unit forms an ordered crystal stacking structure through non-covalent intermolecular interaction connection, so that severe experimental conditions (such as high temperature and high pressure) commonly adopted in chemical bond synthesis are avoided, the organic eutectic structure unit not only inherits the characteristics of light weight, strong solution processability, low cost, but also has the advantages of single crystal of long-range order, high performance, minimum defects and the like, and has the advantages of more abundant composition, more controllable intermolecular acting force design and more various functions (Sun L, zhu W, zhang X, et al creating organic functional materials beyond chemical bond synthesis by organic cocrystal engineering J.am. Chem. Soc.,2021,143,19243-19256). Organic co-crystals that combine two or more different components in the same crystal lattice tend to exhibit novel properties in synergy with various non-covalent interactions, and more researchers have recently begun to focus on the use of organic co-crystals in the photovoltaic field (Yu P, zhen Y, dong H, et al crystal engineering of organic optoelectronic materials. Chem,2019,5,2814-2853). However, eutectic crystals with high photocurrent response and electrochemiluminescence properties have not been reported.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide an organic eutectic synthesis method with photoelectric response performance and application thereof. The novel organic eutectic prepared by the method has rich cation free radicals without external light excitation under dark conditions, has good photocurrent response, high-efficiency cathode electrochemiluminescence performance without external co-reactant, avoids the use of external co-reactant with larger toxicity in the prior art, has the advantages of simple synthesis, ordered structure, high luminous efficiency and good stability, is favorable for sensitive analysis and environmental protection, and has good application prospect in the fields of semiconductor materials, photoelectric parts, environmental detection, biological analysis and the like.
The invention is realized by the following technical scheme:
the invention provides an organic eutectic synthesis method with photoelectric response performance, which comprises the following steps:
and (3) co-crystallizing the 7, 8-tetracyanoquinodimethane with carbazole, dibenzothiophene and dibenzofuran respectively to prepare three organic eutectic Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ.
Further, the molar ratio of the 7, 8-tetracyano-terephthalquinone dimethane to carbazole, dibenzothiophene and dibenzofuran is 1:1.
Further, the method of co-crystallization is a solid sublimation method, specifically: uniformly mixing 7, 8-tetracyanoquinodimethane with carbazole, dibenzothiophene and dibenzofuran respectively, then slowly heating to 200 ℃, keeping for 20min, and then slowly cooling to room temperature.
Further, the temperature rising rate of the slow temperature rising is 6 ℃/min, and the cooling rate of the slow cooling is 5 ℃/min.
The organic eutectic with photoelectric response performance prepared by the method is applied to photocurrent response and electrochemiluminescence.
Further, after the organic eutectic, naphthol, N-dimethylformamide and water are mixed and ground, the obtained mixture is dripped on the surface of a conductive glass electrode, and after drying, eutectic modified conductive glass electrodes Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO are obtained, and are used as working electrodes, are placed in sodium sulfate aqueous solution together with a reference electrode and a counter electrode, and can activate photocurrent response under the action of electric field force.
Further, the concentration of the sodium sulfate aqueous solution was 0.1M.
Further, the organic eutectic is ultrasonically dispersed in N, N-dimethylformamide, the obtained eutectic solution is dripped on the surface of a glassy carbon electrode, and after the eutectic solution is dried, the eutectic modified glassy carbon electrodes Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE are obtained, and are used as working electrodes and are placed in phosphate buffer together with a reference electrode and a counter electrode, so that the cathode electrochemical luminescence performance with high efficiency is achieved without adding a co-reactant.
Further, the phosphate buffer concentration was 0.1. 0.1M, pH to 7.5, containing 0.1M potassium chloride.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides an organic eutectic synthesis method with ultrahigh photocurrent response, and the prepared organic eutectic has rich cationic free radical species when no external energy is excited.
(2) The novel organic eutectic prepared by the method has good photoelectric characteristics, stable photocurrent response, strong repeatability and good application prospect.
(3) The cation organic eutectic provided by the invention has high-efficiency electrochemiluminescence performance, any monomer constituting the eutectic does not have electrochemiluminescence response, the problem that an organic luminophor is quenched in an aqueous medium is avoided, and the luminescence mechanism of the organic eutectic is disclosed.
(4) The invention takes the dissolved oxygen in the system as the electrochemiluminescence amplifying agent to replace the traditional exogenous coreactant with larger toxicity, thereby being beneficial to sensitive analysis and environmental protection.
Drawings
FIG. 1 is an SEM of the co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ.
FIG. 2 shows the intermolecular interactions of co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ and the molecular stacking patterns perpendicular to the a-axis, b-axis and c-axis, respectively; the dashed lines represent the dominant interatomic forces.
FIG. 3 shows the molecular structures of co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ and the intermolecular interactions by independent gradient model analysis.
FIG. 4 is a comparison between XRD experimental values (upper), simulated stacking mode (middle) and Bragg positions (lower) for co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ.
FIG. 5 is an EPR plot of co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ under dark conditions.
FIG. 6 is a graph of photocurrent response of the eutectic Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO systems. Test solution: 0.1M sodium sulfate electrolyte solution, light source 350W xenon lamp.
FIG. 7 is an EIS diagram of cocrystals Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE.
FIG. 8 is an ECL-potential diagram of eutectic Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE systems. Test solution: A0.1M phosphate buffer, pH 7.5, contained 0.1M potassium chloride. Test conditions: the scanning speed is 100mV/s, the scanning range is-3V-0V (vs. Ag/AgCl), and the voltage of the photomultiplier tube is 800V.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1: preparation and characterization of organic Co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ
Uniformly mixing 7, 8-Tetracyanoquinodimethane (TCNQ) with carbazole (Dcz), dibenzothiophene (Dtp) and dibenzofuran (Dfr) respectively in a molar ratio of 1:1 (the mass ratio of TCNQ to Dcz is 204:167, the mass ratio of TCNQ to Dtp is 204:184, and the mass ratio of TCNQ to Dfr is 204:168), sealing, placing into an oven, heating from room temperature to 200 ℃ at a heating rate of 6 ℃/min, then maintaining for 20min, cooling to room temperature at a cooling rate of 5 ℃/min to obtain dark solid, and grinding to obtain eutectic Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ.
The morphology of the prepared co-crystals was characterized using a Scanning Electron Microscope (SEM) and FIG. 1 is an SEM image of the co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ. As can be seen from fig. 1, by means of a high degree of synthesis control, in particular of the interlayer stacking and layer planarity, uniformly distributed needle-like crystals are formed.
The crystal structure was further analyzed by single crystal X-ray diffraction (XRD), and fig. 2 shows the intermolecular interactions of the co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ and the molecular stacking patterns perpendicular to the a-axis, b-axis and c-axis, respectively. As can be seen from FIG. 2, the prepared eutectic is all in C 2 Space group crystallization, electron-deficient acceptor TCNQ and donors Dcz, dtp and Dfr, respectively, form a closely packed stack in ABAB alternating stack pattern.
Direct intermolecular interactions in the co-crystals were characterized using independent gradient model visual analysis, and fig. 3 shows the molecular structures of co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ and intermolecular interactions obtained by independent gradient model analysis. As can be seen from FIG. 3, the co-crystals synthesized by the method of the present invention all undergo molecular recognition by intermolecular strong pi-pi interactions and donor-acceptor interactions and form a eutectic supermolecular network.
FIG. 4 is a comparison between XRD experimental values (upper), simulated stacking mode (middle) and Bragg positions (lower) for co-crystals Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ. As can be seen from FIG. 4, the XRD patterns of the eutectic powder are well consistent with those obtained by simulation, which shows that the eutectic Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ with clear structure, orderly stacking and high crystallinity are successfully prepared by the method of the invention.
FIG. 5 is a solid state electron spin resonance (EPR) plot of co-crystals Dcz-TCNQ, dtp-TCNQ, and Dfr-TCNQ under dark conditions. As can be seen from fig. 5, the EPR plot shows a broad single peak, indicating that the crystal itself is rich in free radical cation species, in an amount that follows the N-containing eutectic (Dcz-TCNQ) > S-containing eutectic (Dtp-TCNQ) > O-containing eutectic (Dfr-TCNQ). Very few reports on free radical crystals are currently reported, taeyeon Kwon et al report that 9, 10-bis (phenylacetylene) phenanthrene synthesizes a high-conductivity organic free radical single crystal through electrochemical crystallization, and when the free radical crystals are formed, molecular orbital energy levels overlap with each other to form a smaller band gap than that of a neutral crystal, and the method is hopefully applied to organic field effect transistors, photovoltaic devices, organic light emitting diodes and sensors (Taeyeon Kwon, jin Young Koo, and Hee Cheul Choi, highly Conducting and Flexible Radical crystals. The invention provides a synthesis method for obtaining stable free radical eutectic through a solid sublimation method for the first time.
Example 2: characterization of the photoelectric response of organic Co-crystals Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO
Sequentially ultrasonically cleaning an Indium Tin Oxide (ITO) conductive glass electrode by using acetone, ethanol and water for 20min, respectively mixing and grinding 50mg of eutectic powder with 40 mu L of naphthol, 40 mu L of N, N-dimethylformamide and 1mL of distilled water for 30min, taking 100 mu L of mixed solution to coat the surface of the conductive glass, and drying at 180 ℃ for 2h to obtain eutectic modified conductive glass electrodes Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO. The prepared eutectic modified conductive glass electrode is used as a working electrode, the working electrode, a reference electrode and a counter electrode are placed in 0.1M sodium sulfate aqueous solution together, a 350W xenon lamp is used as a light source, and a CHI 660 type electrochemical workstation is used for testing photocurrent of the working electrode.
FIG. 6 is a graph showing photocurrent response curves of Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO systems constructed by the method of the present invention. As can be seen from FIG. 6, the three eutectic crystals have strong and stable photocurrent response within 6 cycles>5μA/cm 3 ) The intensity follows that of N-containing eutectic (Dcz-TCNQ/ITO)>S-eutectic (Dtp-TCNQ/ITO)>Containing O-eutectic (Dfr-TCNQ/ITO). Photocurrent is a powerful tool for characterizing the collection and migration capabilities of intermittent photogenerated charges, and a high photocurrent response indicates that the eutectic synthesized by the method of the present invention has a lower charge recombination rate and higher charge transfer efficiency.
Conductivity and charge transfer capacity were further assessed using Electrochemical Impedance Spectroscopy (EIS), and FIG. 7 is an EIS diagram of eutectic modified glassy carbon electrodes Dcz-TCNQ/GCE, dtp-TCNQ/GCE, and Dfr-TCNQ/GCE. As can be seen from fig. 7, the three co-crystals all have a small Nyquist semicircle radius, meaning that the co-crystals have a smaller electrochemical resistance and a higher charge transfer capacity, which is advantageous for charge transfer during the optoelectronic process.
The results show that the eutectic system introduced by the hetero atoms shows excellent characteristics on light absorption and charge transfer capacity related to photoelectric conversion, and the difference between different hetero atoms is beneficial to realizing simple regulation and control of the performance of the photoelectric device.
Example 3: electrochemiluminescence applications with electro-optical response organic co-crystals Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE
Wiping the surface of a Glassy Carbon Electrode (GCE) by using filter paper soaked by ultrapure water, polishing on chamois leather containing alumina paste with the thickness of 1.0 mu M, 0.3 mu M and 0.05 mu M respectively until the surface of the GCE is mirror, respectively placing the electrode in 0.1M nitric acid, absolute ethyl alcohol and ultrapure water for cleaning for 1 minute, and drying the surface of the electrode by using nitrogen gas; dispersing and ultrasonic the prepared eutectic by using N, N-dimethylformamide to obtain a eutectic solution with the concentration of 1 mM; 10 mu L of DMF solutions of Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ with the concentration of 1mM are dripped on the surface of the treated clean GCE, and the treated clean GCE is naturally dried at room temperature to obtain eutectic modified GCE, namely Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE. The prepared eutectic modification GCE is used as a working electrode, the working electrode, a reference electrode and a counter electrode are placed in a phosphate buffer solution with the pH of 0.1M and the pH of 7.5 and containing 0.1M potassium chloride, and an MPI-E type electrochemiluminescence detector is adopted to test an electrochemiluminescence signal of the working electrode within a potential range of-3.0-0V.
FIG. 8 is an Electrochemiluminescence (ECL) -potential diagram of Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE systems constructed by the methods of the present invention. As can be seen from FIG. 8, dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE had significant cathodic ECL signal with a highest ECL efficiency of 82.6% (Dcz-TCNQ/GCE) without any co-reactant addition. However, under the same experimental conditions, neither GCE nor each monomer had a significant ECL signal, indicating that ECL signal was not from a solution or some monomer constituting the co-crystal.
ECL luminescence mechanisms of Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE systems were explored and explained. At the cathode, electrons are input into the acceptor TCNQ unit of the eutectic from the electrode surface to generate anion free radicals (A -· ) The eutectic extended lattice forms a 3D network of free radical transport, which itself has cationic free radicals (D +· ) And electroreduction of the newly formed anion A -· The charge transfer excited state is generated by rapid annihilation therebetween, and luminescence is generated by returning to the ground state in ECL form. In addition, the dissolved oxygen in the system can also be electrochemically reduced into O 2 -· The oxidation-reduction reaction with the cationic eutectic generates a eutectic in an excited state, and the ECL signal of the eutectic is amplified. Thereafter, O 2 -· The ground state eutectic is also oxidized to continue to generate cationic free radicals to participate in luminescence, thereby obtaining a stable and recyclable ECL signal.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in more detail and are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art, and any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (4)
1. The organic eutectic synthesis method with photoelectric response performance is characterized by comprising the following steps:
co-crystallizing 7, 8-tetracyanoquinodimethane with carbazole, dibenzothiophene and dibenzofuran respectively to obtain three organic eutectic Dcz-TCNQ, dtp-TCNQ and Dfr-TCNQ;
wherein, the molar ratio of the 7, 8-tetracyano-terephthalquinone dimethane to carbazole, dibenzothiophene and dibenzofuran is 1:1, and the co-crystallization method is a solid sublimation method, specifically: uniformly mixing 7, 8-tetracyano terephthaloquinone dimethane with carbazole, dibenzothiophene and dibenzofuran respectively, slowly heating to 200 ℃, keeping for 20min, and then slowly cooling to room temperature, wherein the temperature rising rate of the slow heating is 6 ℃/min, and the cooling rate of the slow cooling is 5 ℃/min.
2. The method of claim 1, wherein the organic eutectic with photoelectric response property is used in photocurrent response and electrochemiluminescence.
3. The application of the organic eutectic with photoelectric response performance according to claim 2, wherein after the organic eutectic is mixed and ground with naphthol, N-dimethylformamide and water, the obtained mixture is dripped on the surface of a conductive glass electrode, and after the mixture is dried, eutectic modified conductive glass electrodes Dcz-TCNQ/ITO, dtp-TCNQ/ITO and Dfr-TCNQ/ITO are obtained, and are used as working electrodes, are placed in a sodium sulfate aqueous solution together with a reference electrode and a counter electrode, and can activate photocurrent response under the action of electric field force.
4. The application of the organic eutectic with photoelectric response performance according to claim 2, wherein the organic eutectic is ultrasonically dispersed in N, N-dimethylformamide, the obtained eutectic solution is dripped on the surface of a glassy carbon electrode, and after the eutectic solution is dried, the eutectic modified glassy carbon electrodes Dcz-TCNQ/GCE, dtp-TCNQ/GCE and Dfr-TCNQ/GCE are obtained, are used as working electrodes, are placed in phosphate buffer together with a reference electrode and a counter electrode, and have high-efficiency cathode electrochemical luminescence performance without adding a co-reactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210630502.7A CN115125612B (en) | 2022-06-06 | 2022-06-06 | Organic eutectic synthesis method with photoelectric response performance and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210630502.7A CN115125612B (en) | 2022-06-06 | 2022-06-06 | Organic eutectic synthesis method with photoelectric response performance and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115125612A CN115125612A (en) | 2022-09-30 |
| CN115125612B true CN115125612B (en) | 2024-03-29 |
Family
ID=83377698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210630502.7A Active CN115125612B (en) | 2022-06-06 | 2022-06-06 | Organic eutectic synthesis method with photoelectric response performance and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115125612B (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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109752417A (en) * | 2018-12-25 | 2019-05-14 | 中国科学院上海微系统与信息技术研究所 | A method of detection Clodronate diethylester gas and/or Schain poison gas based on charge-transfer complex |
| CN110350085A (en) * | 2019-07-12 | 2019-10-18 | 中国科学院化学研究所 | A kind of organic eutectic field effect transistor and preparation method thereof |
| CN111912888A (en) * | 2020-07-09 | 2020-11-10 | 湖南师范大学 | Electrochemiluminescence sensor based on eutectic micro-nano material and preparation method and application thereof |
-
2022
- 2022-06-06 CN CN202210630502.7A patent/CN115125612B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109752417A (en) * | 2018-12-25 | 2019-05-14 | 中国科学院上海微系统与信息技术研究所 | A method of detection Clodronate diethylester gas and/or Schain poison gas based on charge-transfer complex |
| CN110350085A (en) * | 2019-07-12 | 2019-10-18 | 中国科学院化学研究所 | A kind of organic eutectic field effect transistor and preparation method thereof |
| CN111912888A (en) * | 2020-07-09 | 2020-11-10 | 湖南师范大学 | Electrochemiluminescence sensor based on eutectic micro-nano material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Near-infrared photothermal conversion properties of carbazole-based cocrystals with different degrees of charge transfer;Pan Shi, et al.;《CrystEngComm》;第24卷;第4622-4628页 * |
| Pan Shi, et al..Near-infrared photothermal conversion properties of carbazole-based cocrystals with different degrees of charge transfer.《CrystEngComm》.2022,第24卷第4622-4628页. * |
| The Structure of the 1 : 1 Molecular Complex of Dibenzothiophene and 7,7,8,8-Tetracyanoquinodimethane.《Acta Cryst.》.1981,第B37卷第1848-1852页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115125612A (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107337644B (en) | A kind of functionalization perovskite material based on ionic liquid and its application in solar battery preparation | |
| Liu et al. | Electrochemically active nanocrystalline SnO2 films: surface modification with thiazine and oxazine dye aggregates | |
| CN101362863B (en) | Triphenyl amine dyes for dye-sensitized solar cells | |
| CN115125612B (en) | Organic eutectic synthesis method with photoelectric response performance and application | |
| CN110346438B (en) | Based on PbS/Co3O4Preparation method of composite signal attenuation type photoelectrochemical immunosensor | |
| CN110054638B (en) | Copper-iodine hybrid semiconductor material and photoelectric application thereof | |
| Wang et al. | Molecularly imprinted photoelectrochemical sensor for aflatoxin B1 detection based on organic/inorganic hybrid nanorod arrays | |
| Wu et al. | Advances in electrochemiluminescence luminophores based on small organic molecules for biosensing | |
| Sun et al. | Two new armtype polyoxometalates grafted on titanium dioxide films: towards enhanced photoelectrochemical performance | |
| CN109439323A (en) | Beta oxidation Asia lead quantum dot and preparation method thereof, photodetector and preparation method thereof | |
| CN113130764A (en) | Zero-bias high-sensitivity perovskite single crystal X-ray detector and preparation method thereof | |
| Tian et al. | Long-range ordered amino acid assemblies exhibit effective optical-to-electrical transduction and stable photoluminescence | |
| CN105384916B (en) | The preparation method and PhotoelectrochemicalProperties Properties of thienyl-containing monokaryon ruthenium complex electropolymerization film | |
| CN108409636A (en) | A kind of structure, synthesis and its application of carbazoles small molecule hole transport material | |
| Li et al. | Photoelectric conversion based on peptide–porphyrin conjugates assembled hydrogel | |
| CN108987117A (en) | CoSe2The preparation method of electrocatalysis material and its application in two-sided quasi-solid-state dye sensitized solar battery | |
| Schlettwein et al. | Influence of polymer matrices on the photoelectrochemical properties of a molecular semiconductor by structural modification | |
| CN110294855B (en) | Ruthenium (II) complex 3D electropolymerization film based on thiophene functionalization | |
| CN107759622A (en) | A kind of triphendioxazine acid imide diploid compound and preparation method thereof | |
| Milic | Perfluoroarenes: A Versatile Platform for Hybrid Perovskite Photovoltaics | |
| Hohman et al. | Covalently attached dianions as sensitizers for photogalvanic effects at semiconductor electrodes | |
| Zhu et al. | Effective photocurrent generation in supramolecular porphyrin-fullerene conjugates assembled by crown ether-alkyl ammonium cation interactions | |
| CN113804736A (en) | Preparation method and application of bismuth/bismuth-oxygen-selenium metal semiconductor heterojunction | |
| Zhang et al. | Photoelectric response of ITO electrode sensitized by single-layer C60-aminodicarboxylate derivative C60 (C7H13NO4) | |
| KR101475702B1 (en) | Opto-electronic Electrode for Solar Cell Comprising Ba-Sn-O Semiconductor Film |
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 |