CN113046075B - Optical metal-based modified gel and preparation method and application thereof - Google Patents

Optical metal-based modified gel and preparation method and application thereof Download PDF

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CN113046075B
CN113046075B CN202110331318.8A CN202110331318A CN113046075B CN 113046075 B CN113046075 B CN 113046075B CN 202110331318 A CN202110331318 A CN 202110331318A CN 113046075 B CN113046075 B CN 113046075B
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CN113046075A (en
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王晓英
李淋雨
顾璇
于秉佳
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides

Abstract

The invention relates to the field of photoelectric material manufacturing, in particular to an optical metal-based modified gel and a preparation method and application thereof, and the following scheme is proposed, wherein the preparation method comprises the steps of adding a salt solution containing metal X ions into a CNS solution subjected to programmed temperature rise, stirring at constant temperature, and synthesizing the CNS by the following steps: the steps comprise firstly g-C3N4Dispersing the powder in water, ultrasonic peeling, centrifuging, and drying to obtain CNS, g-C3N4Is synthesized by the following steps: the method comprises the steps of selecting a compound containing a triazine structure as a reaction precursor, and calcining to obtain g-C3N4. The ECL of the optical metal-based modified gel prepared by the method has the advantages of high strength, low cost, high photoelectric efficiency, good stability, large specific surface area and high electron transfer rate, and has wide application prospect in the fields of photoelectronic devices, marking materials, molecular sensing and biomedical science.

Description

Optical metal-based modified gel and preparation method and application thereof
Technical Field
The invention relates to the field of photoelectric material manufacturing, in particular to an optical metal-based modified gel and a preparation method and application thereof.
Background
Electrochemiluminescence (ECL) has the unique advantages of low background signal, high sensitivity and quick response, and is currently an excellent analysis method applied to researches such as trace target detection, clinical diagnosis, environment and food monitoring of biomolecules, and common ECL active substances comprise quantum dots, luminol and ruthenium bipyridine (ru (bpy))3 2+) And derivatives thereof, wherein Ru (bpy)3 2+The most commonly used ECL luminophores are due to their high luminous efficiency, reversible electrochemical behavior and good chemical stability, but the high cost makes Ru (bpy)3 2+Is limited in its wide application.
The Metal Organic Gel (MOG) is used as an intelligent coordination polymer soft material, and has a porous structure, a large specific surface area, excellent mechanical and chemical stability and a simple and mild preparation method, so that MOG is directly used as a luminous body to be applied to the construction of an ECL sensor in some reports at present, but pyridine derivatives and trimesic acid are mostly used as organic ligands, so that the environmental and water pollution is caused, and the serious harm is caused to the human health.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an optical metal-based modified gel and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of optical metal-based modified gel comprises the following steps:
adding the salt solution containing the metal X ions into the CNS solution after the temperature programming and stirring at constant temperature.
The X comprises at least one metal of alkali metal, alkaline earth metal, transition metal, Al and Pb, and the salt solution containing the metal X ions comprises at least one salt solution of nitrate solution, sulfate solution and halide solution containing the metal X ions.
The CNS is synthesized by:
the steps comprise firstly g-C3N4And dispersing the powder in water for ultrasonic stripping, centrifuging and drying to obtain the CNS.
Further, the g-C3N4Is synthesized by the following steps:
the method comprises the steps of selecting a compound containing a triazine structure as a reaction precursor, and calcining to obtain g-C3N4。
Further, the molar ratio of the metal X ion to the CNS is nX ion:n CNS1 is (1-20) or (1-20) is 1.
Further, the constant-temperature stirring time is 5-80 s.
Further, the rate of the programmed temperature rise is 1-15 ℃/min, and the temperature of the CNS solution after the programmed temperature rise is 10-100 ℃.
Further, the time of ultrasonic stripping is 8-20 h, and the calcining temperature is 550 ℃.
The invention provides an optical metal-based modified gel, which is prepared according to the method.
The invention provides application of the optical metal-based modified gel prepared by the method in the fields of optoelectronic devices, marking materials, molecular sensing and biomedicine.
The invention has the beneficial effects that:
1. the ECL of the optical metal-based modified gel prepared by the method has the advantages of high strength, low cost, high photoelectric efficiency, good stability, large specific surface area and high electron transfer rate;
2. the biocompatibility is good, XCNS (optical metal base modified gel) has a dispersed CNS with a multi-layer ultrathin layer structure, carries a large amount of amino groups with positive charges, and can be directly electrostatically attracted with DNA phosphate frameworks with negative charges and bioactive molecular probes such as protein and enzyme with cysteamine residues; the bioactive molecular probe modified by active groups such as phosphate group, hydroxyl group or carboxyl group can be fixed through covalent bond, in addition, as XCNS contains metal X, the XCNS can be directly combined with biomolecules without adding any coupling agent based on covalent coupling action between metal and biomolecules, and can be widely used as a labeling material;
3. the optical metal-based modified gel obtained can overcome the defects of the existing method by superposing the advantages of the metal nano material and the 2D organic semiconductor material, and the obtained preparation method is simple, quick, green and environment-friendly; the novel photoelectric material has the advantages of remarkably improved luminous efficiency and good conductivity and biocompatibility, can be applied to an ECL biosensor as a luminous active substance, can be used as an electrode modification or labeling material, and provides a way for detecting biomolecules.
Drawings
FIG. 1 is a graph showing the ECL detection curve of AgCNS as a product in the example of the present invention, where A in FIG. 1 is an ECL curve nAgNO3:nCNS1 (1-20), wherein the ECL curve B in FIG. 1 is nAgNO3:nCNSAn ECL detection curve chart of (2-20): 1;
FIG. 2.g-C3N4(A) And FESEM (field emission scanning electron microscope) image of cns (b), FESEM image of AgCNS (C) and its partial enlarged image (D);
FIG. 3 CNS (a), AgNO3(b) And FTIR (Fourier transform Infrared Spectroscopy) plots of AgCNS (c);
FIG. 4.g-C3N4(a) CNS (b) and AgCNS (c) at 100mM K2S2O8ECL profile in 10mM PBS (pH 7.4) (inset: potentials of a, b, c-ECL profile); illustration is shown: AgNO3(i) CNS (ii) and AgCNS (iii) DPV (differential pulse voltammetry) profiles in 10mM PBS (pH 7.4) at a scan rate of 50mV s-1The scanning range is-2.0-2.3V;
FIG. 5 stability study of AgCNS.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
For the sake of simplicity, the description of certain substances according to the invention is in a simplified manner, the specific names or substances being as follows:
g-C3N4refers to graphite-like carbon nitride (graphite-like nitride);
CNS refers to carbon nitride nanoplates (graphite-like carbon nitride nanoethers), which are artificially synthesized compounds with a multi-layered, ultra-thin sheet shape obtained by ultrasonic exfoliation or carboxylation of graphitic carbon nitride; XCNS refers to an optical metal-based modified gel, X refers to a metallic element;
field Emission Scanning Electron Microscopy (FESEM), Differential Pulse Voltammetry (DPV), electrochemiluminescence scanning (ECL), fluorescence inversion microscopy (IFM), fourier transform infrared spectroscopy (FTIR).
Referring to fig. 1 to 5, a method for preparing an optical metal-based modified gel includes the following steps:
adding a salt solution containing metal X ions into a CNS solution which is heated to 10-100 ℃ at a program speed of 1-15 ℃/min, stirring at a constant temperature for 5-80 s, quickly separating from a heat source (within about 2 s), and naturally cooling the obtained product to room temperature in a dark condition for storage.
The X includes one or more of alkali metals (e.g., Na, K, etc.), alkaline earth metals (e.g., Be, Mg, Ca, etc.), transition metals (e.g., Fe, Zr, Co, Cu, Zn, Ti, etc.), and other metals (e.g., Al, Pb, etc.), and may have a valence of +1 (e.g., Na, Pb, etc.) (e.g., Na, K, etc.)+、K+Etc.), +2 valent (e.g., Mg)2+、Cu2+、Ca2+Etc.), +3 valent (e.g., Al)3+、Fe3+Etc.), +4 valent (e.g., Zr)4+、Ti4+Etc.);
the metal X ion-containing salt solution includes a metal X ion-containing nitrate solution (e.g., Ag-containing salt solution)+、Cu2+Nitrate solutions of, e.g. AgNO3、Cu(NO3)2Etc.), sulfate solutions (e.g., containing Co)2+、Cu2+Sulfate solutions of (e.g. CoSO)4、CuSO4Etc.) and a halogen salt solution (e.g., containing Zr)4+、Ca2+、Fe2+Solutions of halide salts, e.g. ZrCl4、CaCl2、FeBr2Etc.) in a saline solution.
The molar ratio of the metal X ion to the CNS is nX ion:n CNS1 is (1-20) or (1-20) is 1.
The g to C3N4Is synthesized by the following steps:
the above-mentionedThe method comprises selecting triazine structure-containing compound (such as cyanuric chloride, melamine, urea, thiourea, etc.) as reaction precursor, calcining at 550 deg.C for 4 hr at 5 deg.C/min by thermal polymerization method to obtain block g-C3N4。
The CNS is synthesized by:
the steps comprise firstly, preparing the block g-C3N4Grinding to obtain powder, mixing g-C3N4And dispersing the powder in water, ultrasonically stripping for 8-20 h, centrifuging and drying to obtain the CNS.
Example one
g-C3N4The synthesis of (2): for example, g-C can be synthesized by thermal polymerization3N4. For example, 5.0g of white melamine powder is placed in a covered ceramic crucible, heated at a rate of 5 ℃/min for 4 hours at 550 ℃ in a muffle furnace, allowed to cool to room temperature naturally, and the resulting yellow block g-C is then ground using an agate mortar3N4Grinding into powder for further use.
Example two
Synthesis of CNS: for example, g-C may be3N4The powder (100mg) was dispersed in 100mL of ultrapure water and ultrasonically peeled off for 12 hours, followed by centrifugation and drying to obtain CNS.
EXAMPLE III
Synthesis of AgCNS: n isAgNO3:nCNS＝1:2
For example, CNS (6.2mg) can be dissolved in 2mL of ultrapure water, the solution programmed to 80 ℃ in a magnetically heated stirrer, and then 10. mu.L of 0.425g/mL AgNO can be added rapidly3And (4) maintaining the temperature, stirring for 30s, quickly removing the heat source (within about 2 s), and preserving after the AgCNS is naturally cooled to room temperature under the condition of keeping away from light.
Example four
Synthesis of AgCNS: n isAgNO3:nCNS＝1:1
For example, CNS (5.3mg) can be dissolved in 2mL of ultrapure water, the solution can be programmed to 80 ℃ in a magnetic heating stirrer, and then 10. mu.L of,0.815g/mL AgNO3And (4) maintaining the temperature, stirring for 30s, quickly removing the heat source (within about 2 s), and preserving after the AgCNS is naturally cooled to room temperature under the condition of keeping away from light.
EXAMPLE five
Synthesis of AgCNS: n isAgNO3:nCNS＝1:20
For example, CNS (18.6mg) can be dissolved in 2mL of ultrapure water, the solution programmed to 80 ℃ in a magnetically heated stirrer, and then 10. mu.L of 0.165g/mL AgNO can be added rapidly3And (4) maintaining the temperature, stirring for 30s, quickly removing the heat source (within about 2 s), and preserving after the AgCNS is naturally cooled to room temperature under the condition of keeping away from light.
EXAMPLE six
Synthesis of AgCNS: n isAgNO3:nCNS＝2:1
For example, CNS (3.2mg) can be dissolved in 2mL of ultrapure water, the solution programmed to 80 ℃ in a magnetically heated stirrer, and then 10. mu.L of 1.12g/mL AgNO can be added rapidly3And (4) maintaining the temperature, stirring for 30s, quickly removing the heat source (within about 2 s), and preserving after the AgCNS is naturally cooled to room temperature under the condition of keeping away from light.
EXAMPLE seven
Synthesis of AgCNS: n isAgNO3:nCNS＝20:1
For example, CNS (1.1mg) can be dissolved in 2mL of ultrapure water, the solution programmed to 80 ℃ in a magnetically heated stirrer, and then 10. mu.L of 3.856g/mL AgNO can be added rapidly3And (4) maintaining the temperature, stirring for 30s, quickly removing the heat source (within about 2 s), and preserving after the AgCNS is naturally cooled to room temperature under the condition of keeping away from light.
ECL detection of AgCNS
ECL detection is carried out on the product AgCNS prepared in the third embodiment, 8 mu L of AgCNS is dripped on the surface of a Glassy Carbon Electrode (GCE), and the AgCNS is dried and used for ECL detection;
ECL detection condition setting: a one-chamber three-electrode system was used, with a glassy carbon electrode (GCE, diameter 3.0mm) as the working electrode, a platinum wire electrode (Pt) as the counter electrode, and an Ag/AgCl (saturated KCl solution) as the reference electrode, in the presence ofHas a molecular weight of 100mmol/L K2S2O8ECL detection was performed in 10mmol/L PBS (pH 7.4) as a co-reagent. Applying a cyclic voltammetry scan mode negative scan at a rate of 100mV/s over a continuous potential scan range of-0.2 to-1.8V, applying a photomultiplier tube pressure of 600V with a magnification factor set to 3, and simultaneously recording an ECL curve, as shown in FIG. 1;
the ECL curve of A in FIG. 1 is nAgNO3:n CNS1, (1-20), and the curves from left to right correspond to the molar ratio from top to bottom in the upper right part of the graph;
the ECL curve of B in FIG. 1 is nAgNO3:nCNSThe ECL detection curve chart of (2-20): 1, and the curves from left to right sequentially correspond to the molar ratio from top to bottom at the lower right in the graph;
as can be seen from FIG. 1, when AgNO is immobilized3Amount of substance (n)AgNO3) Is 1, nCNSDuring the transition from 1 to 20, the synthetic AgCNS retains some ECL signal, but at nAgNO3:nCNSThe ECL signal value is maximal at 1:2, and is about 11500 a.u.;
when n is fixedCNSTo 1, change nAgNO3In the amount of (1), with nAgNO3During the transition from 1 to 20, the synthetic AgCNS retains some ECL signal, but at nAgNO3:nCNSAt 10:1, the ECL signal value was maximal, about 7350 a.u.;
7350a.u.<11500a.u, it is found that the optimum ratio of synthesized AgCNS is nAgNO3:nCNSAgCNS exhibits excellent luminescence properties as 1: 2.
For g-C3N4CNS and AgCNS have been characterized by microscopic morphology, respectively, from g-C3N4It can be seen from the Field Emission Scanning Electron Microscopy (FESEM) (A in FIG. 2) that g-C3N4A multilayer sheet structure with a curled stack is presented, and the surface is rough;
when g-C3N4After the CNS is formed by ultrasonic stripping treatment (B in figure 2), a dispersed thin-layer multilayer sheet structure is presented, and the surface is smooth;
relative to g-C3N4The sonicated CNS has a more dispersed multi-layered ultrathin lamellar structure and a larger specific surface area, which adsorbs higher amounts of oxygen than bulk g-C3N4And protonation of the CNS causes its CN heterocycle and cyano group to be positively charged, based on quantum confinement effects, the bulk g-C3N4The CNS exhibits a large band gap and a blue shift of the fluorescence peak, with the band gap energy increasing with decreasing thickness, the CNS can provide appropriate spatial separation and porous structure to achieve high permeability of the co-reactant, can accelerate electron migration, promote the formation of CNS excited states, cause a significant negative shift in the ECL onset voltage, and enhance the photoelectric efficiency;
g-C without ultrasonic stripping3N4Respectively with triazine ring (C)3N3) And 3-s-triazine ring (C)6N7) The two-dimensional nanosheet layers are bonded by van der waals forces for infinite extension of the basic structural unit to form a network structure, and although the 3-s-triazine structure is energetically more stable than triazine, both contain hydrogen atoms present as amine groups due to incomplete condensation, the presence of hydrogen atoms on the terminal edges introduces many surface defects, and the defect sites are incorporated into g-C by doping metal ions to bind carbon and nitrogen vacancies3N4In the network, the optical band gap can be reduced to improve light absorption, the electron transfer rate can be improved by doping metal ions, and the metal ions promote g-C through coordination3N4Charge transfer and recombination between unit excited states, so that metal ions are stripped from g-C by ultrasonic3N4After the CNS binding later obtained, the finally formed XCNS exhibits enhanced ECL signal due to the superposition of dominance, and in addition, with K2S2O8As a co-reactant, the metal ion can accelerate S2O8 2-Electrocatalytic reduction of (ii) to produce more SO4 ·-Free radical, thereby further improving ECL strength, with Ag+For example, take K2S2O8The mechanism of AgCNS luminescence when used as a co-reagent is as follows:
S2O8 2-+e-→SO4 ·-+SO4 2-
Ag(I)CNS+S2O8 2-+e-→Ag(II)CNS+SO4 ·-+SO4 2-
Ag(II)CNS+SO4 ·-→Ag(I)CNS*+SO4 2-
Ag(I)CNS*→Ag(I)CNS+hv
thus, an optically metal-based modified gel (e.g., AgCNS) prepared using the methods provided herein can result in enhanced ECL signaling with significantly increased photoelectric efficiency;
XCNS retains the excellent electron transfer capacity of metal ions, and CNS and metal ions are connected through coordination, thereby providing an electron 'expressway' for rapid electron transfer through the interface, accelerating the electron transfer rate, and the large specific surface area of CNS is beneficial to coordination with more metal ions, thereby showing good conductive performance;
the invention provides an optical metal-based modified gel, which is prepared according to the method.
AgCNS (C in fig. 2) prepared by doping CNS with metal elements by the method of the present invention, which exhibits irregular polyhedral shape, rough surface and shows 3D porous structure, which is uniformly distributed on the surface of AgCNS as seen from enlarged spectrum (D in fig. 2), and which has an average size of about 80 ± 10 nm;
analysis of pure CNS, AgNO by FTIR Spectroscopy3And AgCNS, as shown in FIG. 3, all show a series of multiple bands, as shown by curve a, and the FT-IR spectrum of the CNS shows a spectrum at 1200-1600 cm–1Vibration of the area (1230, 1310, 1456, 1535 and 1628cm–1) Typical stretching modes corresponding to CN heterocycles, such as C-N and C ═ N stretching; 885cm–1The wave band at which corresponds to the flexural vibration of the CN heterocycle, 3000-3500 cm–1The broad peak of vibration of (a) is caused by tensile vibration of the primary amine;
AgNO3has an FTIR spectrum (curve b) at 1375, 1441cm–1A characteristic peak appears, probably due to-NO3Is caused by stretching and bending. From the FTIR spectrum of AgCNS (curve c) it was shown that AgNO was retained3Characteristic peaks of the CNS, therefore, the above data confirm the successful synthesis of AgCNS;
characterization of the prepared AgCNS by Differential Pulsed Voltammetry (DPV), electrochemiluminescence scanning (ECL), and fluorescence inverted microscope (IFM), g-C alone, was performed separately3N4Only weak ECL signal (fig. 4, curve a), which is further enhanced after ultrasound to form CNS with dispersed structure (fig. 4, curve b), AgCNS prepared by doping CNS with metal elements by the method of the invention, which exhibits the strongest ECL signal (fig. 4, curve c);
in the DPV curves (inset in FIG. 4), it is clearly observed that AgCNS has separate current peaks (curve iii) at potentials of approximately +0.2V and-1.3V (vs. Ag/AgCl), respectively, and AgNO peaks at potential positions of +0.2V and-1.3V, respectively3(curve i) and characteristic peaks of the CNS (curve ii);
the IFM plot shows that AgCNS exhibits irregular tetrahedral shape and emits bright blue light, and furthermore, AgCNS produces an emission wavelength at 460nm with an intensity of about 240a.u. when the excitation wavelength is set at 350nm, indicating that it retains good optical properties in the composite structure;
in the method, XCNS is formed by combining programmed heating with magnetic stirring, higher temperature can promote the combination of metal ions and CNS, because the metal ions can accelerate molecular collision and thus accelerate the coordination of the metal ions and the CNS, the raw materials can be fully contacted and the reaction time is shortened by the programmed heating in the process of magnetic stirring, the XCNS formed after the programmed heating is quickly separated from a heat source for cooling, the air condensation rate is accelerated, and the time for forming XCNS is shortened;
XCNS has a dispersed multi-layer ultrathin sheet structure CNS, which carries a large amount of positively charged amino groups, and can be directly electrostatically attracted with negatively charged DNA phosphate skeleton, protein with cysteamine residues, enzyme and other bioactive molecular probes;
the bioactive molecular probe modified by active groups such as phosphate group, hydroxyl group or carboxyl group can be fixed through covalent bond, in addition, as XCNS contains metal X and can be directly combined with biomolecules without adding any coupling agent based on covalent coupling action between metal and biomolecules, the material has better biocompatibility and can be widely used as a labeling material;
the stability of the material is also an important factor influencing the ECL performance, the AgCNS is fixed on the electrode as an electrode modification material, and is measured after being stored at 4 ℃ for 1,3,5,7,9,11,13,15,17,19,21,23 and 25 days, respectively, and the obtained data is shown in fig. 5, the stability does not change much at the end of the first week, the ECL signal value at 15 days is about 95.6% of that of a freshly prepared electrode, and is reduced to less than 89.5% after 23 days, and the results show that the ECL biosensor using the AgCNS as a signal marker shows excellent stability;
because of g-C3N4As a novel ECL active matter, the ECL active matter has higher chemical stability and thermal stability, g-C3N4The CNS of the multi-layer ultrathin sheet layer formed by ultrasonic treatment has a more dispersed structure, can accelerate electron transfer and promote the formation of CNS excited state, so that ECL initial voltage is obviously negatively shifted, the photoelectric efficiency is enhanced, and the photoelectric efficiency is improved when K is used2S2O8When used as a co-reactant, the metal ion can accelerate S2O8 2-Electrocatalytic reduction of (ii) to produce more SO4 ·-The ECL signal of XCNS with ECL activity formed by CNS and metal ions through coordination is hardly changed after 30 CV cycle scans, which indicates that the XCNS has very good stability, and the ECL signal is hardly changed after being modified on naked GCE and stored in phosphate buffer at 4 ℃ for 15 days, thereby indicating that the stability of AgCNS is better.
The optical metal-based modified gel obtained can overcome the defects of the existing method by superposing the advantages of the metal nano material and the 2D organic semiconductor material, and the obtained preparation method is simple, quick, green and environment-friendly; the novel photoelectric material has the advantages of remarkably improved luminous efficiency and good conductivity and biocompatibility, can be applied to an ECL biosensor as a luminous active substance, can be used as an electrode modification or labeling material, and provides a way for detecting biomolecules.
Therefore, the invention also provides the application of the optical metal-based modified gel prepared by the method in the fields of optoelectronic devices, molecular sensing and biomedicine, for example, the optical metal-based modified gel can be used as a biomolecule marker and an electrode modification material in an ECL biosensor.
Existing AgMOG as a co-reagent had little ECL signal in PBS buffer; even in PBS buffer, the signal value of AgCNS synthesized by the invention can still reach 2500a.u. and AgCNS can also be used as a co-reactant.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.

Claims (8)

1. A preparation method of optical metal-based modified gel is characterized by comprising the following steps: the method comprises the following steps:
adding a salt solution containing metal X ions into the CNS solution after temperature programming and stirring at constant temperature;
the X comprises at least one metal of alkali metal, alkaline earth metal, transition metal, Al and Pb, and the salt solution containing the metal X ions comprises at least one salt solution of nitrate solution, sulfate solution and halide solution containing the metal X ions;
the CNS is synthesized by:
the steps comprise firstly g-C3N4And dispersing the powder in water for ultrasonic stripping, centrifuging and drying to obtain the CNS.
2. According to claim 1The preparation method of the optical metal-based modified gel is characterized in that g-C3N4Is synthesized by the following steps:
the method comprises the steps of selecting a compound containing a triazine structure as a reaction precursor, and calcining to obtain g-C3N4。
3. An optical metal-based modified gel as claimed in claim 2, wherein the molar ratio of metal X ions to CNS is nX ion:nCNSAnd (1) =1 (1-20) or (1-20): 1.
4. The method for preparing optical metal-based modified gel according to claim 3, wherein the constant-temperature stirring time is 5-80 s.
5. The method for preparing an optical metal-based modified gel according to claim 4, wherein the temperature programming rate is 1 ℃/min to 15 ℃/min, and the temperature of the CNS solution after temperature programming is 10 ℃ to 100 ℃.
6. The optical metal-based modified gel and the preparation method thereof according to claim 5, wherein the ultrasonic stripping time is 8-20 h, and the calcining temperature is 550 ℃.
7. An optically metal-based modified gel, characterized in that it is prepared according to the method of any one of claims 1 to 6.
8. Use of the optically metal-based modified gel of claim 7 in the fields of optoelectronic devices, labeling materials, molecular sensing, and biomedical applications.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105067579A (en) * 2015-07-28 2015-11-18 华南师范大学 Preparation and application of single-layer g-C3N4 fluorescence sensor
CN106744744A (en) * 2017-01-20 2017-05-31 济南大学 The preparation method and products therefrom of a kind of cellular graphite phase carbon nitride nano material of cobalt doped

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105067579A (en) * 2015-07-28 2015-11-18 华南师范大学 Preparation and application of single-layer g-C3N4 fluorescence sensor
CN106744744A (en) * 2017-01-20 2017-05-31 济南大学 The preparation method and products therefrom of a kind of cellular graphite phase carbon nitride nano material of cobalt doped

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